Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting(OWS).In this study,a three-dimensional(3D)core-shell structure Co_(3)S_(4)/CuS@NiFe LDH nanocoral ...Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting(OWS).In this study,a three-dimensional(3D)core-shell structure Co_(3)S_(4)/CuS@NiFe LDH nanocoral spheres electrocatalyst was constructed on nickel foam(NF)via an interfacial engineering strategy.This 3D core-shell heterostructure maximizes the exposure of active sites,optimizes the charge transport pathway and accelerates gas release rates.The protective shell strategy of NiFe LDH provides favorable stability,which contributes to inhibiting the electrochemical corrosion of the electrocatalyst and mitigating the toxic effects of Cl−and other microorganisms during the seawater splitting process.Moreover,the introduction of NiFe LDH induces a change in the OER mechanism from an adsorption evolution mechanism(AEM)to a lattice oxygen mechanism(LOM),which improves the intrinsic activity of the catalyst.Consequently,Co_(3)S_(4)/CuS@NiFe LDH demonstrates exceptional performance in the oxygen evolution reaction(OER)(η100=251 mV)and in the hydrogen evolution reaction(HER)(η100=254 mV),alongside remarkable stability over 100 h.For OWS,it exhibits a voltage of 1.46 V at 10 mA/cm^(2) and maintain stability for 100 h.Impressively,Co_(3)S_(4)/CuS@NiFe LDH still possesses outstanding activity and stability in natural alkaline seawater.This work proposes interfacial engineering to construct bifunctional catalysts with core-shell heterostructures,providing instructive guidelines for the design of highly efficient electrocatalysts toward seawater electrolysis.展开更多
Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen e...Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.展开更多
Hydrogen peroxide(H_(2)O_(2)) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection,metal etching,textile printing and dyeing,chemical synthesi...Hydrogen peroxide(H_(2)O_(2)) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection,metal etching,textile printing and dyeing,chemical synthesis and food processing.However,over 90 % of industrial H_(2)O_(2) is currently produced through the multi-step anthraquinone oxidation process,which suffers from a process with some drawbacks such as complex,high-energy consumption,and toxic byproducts emissions.Compared to the traditional anthraquinone method,artificial photosynthesis of H_(2)O_(2) using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O_(2) as the clean reactants and sole energy as the driving force.In recent years,metal-free photocatalysts mainly including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs) and carbon nitrile(g-C_(3)N_(4)) have garnered significant interest due to their superior thermal and chemical stability,diverse synthesis methods,tunable functionality,light weight nature and non-toxicity.These materials also exhibit adjustable band structure and unique photoelectric properties.Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H_(2)O_(2),however,a comprehensive summary of current research status on metalfree-based photocatalytic overall H_(2)O_(2) production remain scarce.This review outlines recent process in overall H_(2)O_(2) photosynthesis based on metal-free photocatalysts.First,we introduced the fundamental concepts of photocatalytic overall H_(2)O_(2) production.Then,we analyze representative studies on photocatalytic overall H_(2)O_(2) synthesis using metal-free materials.Finally,we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H_(2)O_(2) generation.展开更多
The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing...The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing overall water splitting. Here, we developed an innovative heterogeneous interface engineering strategy to boost the electrocatalytic performance of overall water splitting. This approach involves the synergistic integration of ultra‐fine CoMoP nanocrystals coupled with three‐ dimensional (3D) porous C3N4/N‐doped carbon (NC) architectures, constructing a distinctive CoMoP/C3N4/NC heterogeneous interface. The CoMoP/C3N4/NC exhibits distinguished overall water splitting performance. To drive the overall water splitting current of 10 mA cm−2, the CoMoP/C3N4/NC||CoMoP/C3N4/NC electrolysis cell only needs an ultralow cell voltage of 1.496 V. The electronic properties and localized coordination environments characterizations, and density functional theory (DFT) calculations elucidate that the improved catalytic activities of CoMoP/C3N4/NC are primarily attributed to the synergistic interfacial coupling between CoMoP/C3N4/NC heterogeneous interface. A novel multi‐site synergistic catalytic mechanism was revealed by the DFT calculations, in which the optimum H* adsorption site on CoMoP/C3N4/NC for HER is on the cobalt atoms in CoMoP with the ultralow Gibbs free energy of hydrogen bonding (ΔGH*) of 0.018 eV, while for the OER, the optimum intermediates adsorption site of the CoMoP/C3N4/NC is on the carbon atoms in C3N4/NC. Besides, the intricately engineered 3D hierarchical porous framework of the CoMoP/C3N4/NC can facilitate the ion and electron transport and improve mass transfer, which gives rise to enhanced water splitting performance.展开更多
BACKGROUND Esophageal carcinoma(EC)presents a significant public health issue in China,with its prognosis impacted by myriad factors.The creation of a reliable prog-nostic model for the overall survival(OS)of EC patie...BACKGROUND Esophageal carcinoma(EC)presents a significant public health issue in China,with its prognosis impacted by myriad factors.The creation of a reliable prog-nostic model for the overall survival(OS)of EC patients promises to greatly advance the customization of treatment approaches.AIM To create a more systematic and practical model that incorporates clinically significant indicators to support decision-making in clinical settings.METHODS This study utilized data from a prospective longitudinal cohort of 3127 EC patients treated at Chongqing University Cancer Hospital between January 1,2018,and December 12,2020.Utilizing the least absolute shrinkage and selection operator regression alongside multivariate Cox regression analyses helped pinpoint pertinent variables for constructing the model.Its efficacy was assessed by concordance index(C-index),area under the receiver operating characteristic curve(AUC),calibration curves,and decision curve analysis(DCA).RESULTS Nine variables were determined to be significant predictors of OS in EC patients:Body mass index(BMI),Karnofsky performance status,TNM stage,surgery,radiotherapy,chemotherapy,immunotherapy,platelet-to-lymphocyte ratio,and albumin-to-globulin ratio(ALB/GLB).The model demonstrated a C-index of 0.715(95%CI:0.701-0.729)in the training cohort and 0.711(95%CI:0.689-0.732)in the validation cohort.In the training cohort,AUCs for 1-year,3-year,and 5-year OS predictions were 0.773,0.787,and 0.750,respectively;in the validation cohort,they were 0.772,0.768,and 0.723,respectively,illustrating the model's precision.Calibration curves and DCA verified the model's predictive accuracy and net benefit.CONCLUSION A novel prognostic model for determining the OS of EC patients was successfully developed and validated to help clinicians in devising individualized treatment schemes for EC patients.展开更多
BACKGROUND The prevalence and mortality rates of gastric carcinoma are disproportionately elevated in China,with the disease's intricate and varied characteristics further amplifying its health impact.Precise fore...BACKGROUND The prevalence and mortality rates of gastric carcinoma are disproportionately elevated in China,with the disease's intricate and varied characteristics further amplifying its health impact.Precise forecasting of overall survival(OS)is of paramount importance for the clinical management of individuals afflicted with this malignancy.AIM To develop and validate a nomogram model that provides precise gastric cancer prevention and treatment guidance and more accurate survival outcome prediction for patients with gastric carcinoma.METHODS Data analysis was conducted on samples collected from hospitalized gastric cancer patients between 2018 and 2020.Least absolute shrinkage and selection operator,univariate,and multivariate Cox regression analyses were employed to identify independent prognostic factors.A nomogram model was developed to predict gastric cancer patient outcomes.The model's predictability and discriminative ability were evaluated via receiver operating characteristic curves.To evaluate the clinical utility of the model,Kaplan-Meier and decision curve analyses were performed.RESULTS A total of ten independent prognostic factors were identified,including body mass index,tumor-node-metastasis(TNM)stage,radiation,chemotherapy,surgery,albumin,globulin,neutrophil count,lactate dehydrogenase,and platelet-to-lymphocyte ratio.The area under the curve(AUC)values for the 1-,3-,and 5-year survival prediction in the training set were 0.843,0.850,and 0.821,respectively.The AUC values were 0.864,0.820,and 0.786 for the 1-,3-,and 5-year survival prediction in the validation set,respectively.The model exhibited strong discriminative ability,with both the time AUC and time C-index exceeding 0.75.Compared with TNM staging,the model demonstrated superior clinical utility.Ultimately,a nomogram was developed via a web-based interface.CONCLUSION This study established and validated a novel nomogram model for predicting the OS of gastric cancer patients,which demonstrated strong predictive ability.Based on these findings,this model can aid clinicians in implementing personalized interventions for patients with gastric cancer.展开更多
The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting.In this study,NiCo alloy cocatalysts were...The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting.In this study,NiCo alloy cocatalysts were synthesized with nickel/cobalt metal organic framework(NiCo-MOF)as source of nickel and cobalt.Systematic characterization results demonstrate the successful deposition of alloy cocatalysts onto the surface of SrTiO_(3).The prepared SrTiO_(3)loaded NiCo-alloy can generate hydrogen and oxygen in a stoichiometric ratio for photocatalytic overall water splitting,achieving an apparent quantum yield of 11.9%at 350±10 nm.Theoretical calculations indicate that the introduction of cobalt has a beneficial regulatory effect on the hydrogen evolution sites of Ni,reducing the free energy of H adsorption.The synergistic catalytic effect of bimetallic catalysts contributes to enhancing photocatalytic activity and stability.This study offers constructive insights for the development of high-efficiency and cost-effective cocatalyst systems.展开更多
BACKGROUND Rectal cancer is prevalent and associated with substantial morbidity and mortality.AIM To develop a nomogram prediction model for overall survival(OS)in patients with rectal cancer by leveraging a comprehen...BACKGROUND Rectal cancer is prevalent and associated with substantial morbidity and mortality.AIM To develop a nomogram prediction model for overall survival(OS)in patients with rectal cancer by leveraging a comprehensive analysis of demographic,clinicopathological,haematological,and follow-up data to identify independent prognostic factors.METHODS We conducted a prospective cohort study in China involving rectal cancer patients and applied Cox regression and least absolute shrinkage and selection operator regression to assess the significance of various variables as independent prognostic factors for OS.The identified factors were integrated into a nomogram model,which was evaluated for predictive accuracy via the C-index,area under the curve(AUC),calibration curve,and decision curve analysis(DCA).RESULTS Multivariate analysis revealed independent predictors of OS,including the Karnofsky performance status,age,sex,TNM stage,chemotherapy,surgery,targeted therapy,β2-microglobulin,lactate dehydrogenase,and the neutrophil-to-lymphocyte ratio.The nomogram demonstrated a C-index of 0.80 for the training and validation cohorts,with AUC values indicating high predictive accuracy for 1-year,3-year,and 5-year OS.The calibration curves confirmed the model's excellent agreement with the observed survival rates,and DCA revealed the superior clinical utility of the nomogram over the TNM staging system.CONCLUSION In this study,a novel prognostic model that accurately predicts the OS of rectal cancer patients was developed.The model exhibited excellent discriminatory and calibration capabilities,thus offering a reliable tool for health care professionals to estimate patient survival.展开更多
Fixed-wing long-endurance aircraft play an important role in many fields.However,to reduce drag,these aircraft often have an enormous aspect ratio and wingspan,leading to challenges such as high requirements for takeo...Fixed-wing long-endurance aircraft play an important role in many fields.However,to reduce drag,these aircraft often have an enormous aspect ratio and wingspan,leading to challenges such as high requirements for takeoff and landing sites and poor wind resistance.Morphing may be able to solve this problem,but conventional morphing aircraft often employ complex actuation mechanisms and actuators to drive the morphing process.The associated costs in terms of structural weight increase and space occupancy are prohibitively high.First,this article develops a high-aspect-ratio aircraft with aerodynamic-driven morphing and validates the rationality and feasibility of this concept through flight tests.Then,focusing on the RQ-4‘‘Global Hawk”as the design baseline,the article explores multidisciplinary overall design methods for the aircraft,analyzing the comprehensive impact of morphing on aerodynamic,structural,and flight control design.Finally,the article elaborates on the benefits and costs associated with aerodynamic-driven morphing.展开更多
Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of C...Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.展开更多
Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and...Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.展开更多
Exploring earth-abundant,highly active bifunctional electrocatalysts for efficient hydrogen and oxygen evolution is crucial for water splitting.However,due to their distinct free energies and conducting behaviors(elec...Exploring earth-abundant,highly active bifunctional electrocatalysts for efficient hydrogen and oxygen evolution is crucial for water splitting.However,due to their distinct free energies and conducting behaviors(electron/hole),balancing the catalytic efficiency between hydrogen and oxygen evolution remains challenging for achieving bifunctional electrocatalysts.Here,we report a locally-doped MoS_(2)monolayer with an in-plane heterostructure acting as a bifunctional electrocatalyst and apply it to the overall water splitting.In this heterostructure,the core region contains Mo/S vacancies,while the ring region was doped by Fe atoms(in two substitution configurations:1FeMo and 3FeMo-VS clusters)with a p-type conductive characteristic.Our micro-cell measurements,combined with density functional theory(DFT)calculations,reveal that the vacancies-rich core region presents remarkable hydrogen evolution reaction(HER)activity while the Fe-doped ring gives an excellent oxygen evolution reaction(OER)activity,thus forming an in-plane bifunctional electrocatalyst.Finally,as a proof-of-concept for overall water splitting,we constructed a full-cell configuration based on a locally-doped MoS_(2)monolayer,which achieved a cell voltage of 1.87 V at 10 mA·cm^(-2),demonstrating outstanding performance in strong acid electrolytes.Our work provides insight into the hetero-integration of bifunctional electrocatalysts at the atomic level,paving the way for designing transition metal dichalcogenide catalysts with activity-manipulated regions capable of multiple reactions.展开更多
Anion exchange membrane electrolysis (AEMWE) is currently a promising technology to produce hydrogen from water. Developing the highly intrinsic activity of electrodes is extremely important. In this paper, nitrogen v...Anion exchange membrane electrolysis (AEMWE) is currently a promising technology to produce hydrogen from water. Developing the highly intrinsic activity of electrodes is extremely important. In this paper, nitrogen vacancies-rich cobalt nitride (Co_(4)N-VN) is used as the anode catalyst of the urea oxidation reaction (UOR) and its loading Pt (Pt@Co_(4)N-VN) acted as the cathode of hydrogen evolution reaction (HER). The introduction of N-vacancies gained the electron-deficient Co_(4)N more favorable for the UOR process. Meanwhile, the electron transfer between the Co_(4)N-VN carrier and Pt can enhance the intrinsic HER activity of loaded Pt. Specifically, in the 0.33 M urea and 1.0 M KOH electrolyte, the UOR potential of CO_(4)N-VN is only 1.58 V at the current density of 300.0 mA cm^(-2), which is much lower than that of Co_(4) N and Co_(3)O_(4). At the same time, the HER overpotential at 1.0 M KOH and 300.0 mA cm^(-2) is only 120.0 mV, lower than 20 wt% Pt/C. By measuring the bode phase diagram, the presence of N-vacancies can accelerate the electron transfer rate of catalysts to improve the UOR and HER electrocatalytic activity. The overall water-splitting device featuring Pt@Co_(4)N-VN||Co_(4)N-VN electrodes achieves a voltage of 2.99 V at a current density of 300.0 mA cm^(-2).展开更多
Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity durin...Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear.Herein,density functional theory(DFT)calculations first reveal the modulation of sulfur vacancy concentrations on Co_(9)S_(8)electronic structures,predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting.Experimentally fabricated Co_(9)S_(8)with appropriate sulfur vacancies exhibits superior bifunctional activity(HER:164 mV@_(η10);OER:297 mV@_(η100)).The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V(10 mA cm^(−2))for over 60 h.Experimental studies illustrate that sulfur vacancies preferentially adsorb OH^(−)during reactions,inducing the formation of CoOOH active phases.DFT analysis further indicates that OH^(−)adsorption weakens d-p orbital hybridization,optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance.This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics,electronic structures and catalytic performance.展开更多
BACKGROUND Although recent studies have reported the reliability of triglyceride-glucose index(TyG)as a biomarker for evaluation of insulin resistance,the research exploring the association of TyG-body mass index(BMI)...BACKGROUND Although recent studies have reported the reliability of triglyceride-glucose index(TyG)as a biomarker for evaluation of insulin resistance,the research exploring the association of TyG-body mass index(BMI)with major cardiovascular outcomes and all-cause mortality among the type 2 diabetes mellitus(T2DM)population remains scarce.AIM To ascertain whether TyG-BMI correlates with cardiovascular outcomes and mortality risk in individuals diagnosed with T2DM.METHODS Data were drawn from the ACCORD trial and its subsequent follow-up(ACCORDION),which together included 10190 participants.To evaluate the associations of TyG-BMI with future cardiovascular outcomes and overall mortality risk among T2DM patients,Cox’s proportional-hazards model was employed.Non-linear associations and thresholds were investigated by performing restricted cubic spline regression,fitting smooth curves,and conducting piecewise regression.Additionally,we examined whether the above findings were robust through interaction and subgroup analyses.The robustness of results was further verified by a series of sensitivity assessments.Through the area under the receiver operating characteristic curve estimation,the incremental predictive power of TyG-BMI beyond conventional risk factors was also evaluated.RESULTS Applying multivariable Cox regression analysis,we identified a significant correlation of TyG-BMI with both cardiovascular outcomes and overall mortality.Specifically,after adjusting for multiple confounders,the cardiovascular mortality,congestive heart failure(CHF)and overall mortality risks in the highest TyG-BMI quartile were 1.74,2.65 and 1.42 times greater,respectively,when compared to the lowest quartile.The analysis revealed that TyG-BMI was linked nonlinearly to both types of mortality,while a two-stage linear regression discerned inflection points at 252.77 for cardiovascular mortality and 245.90 for overall mortality.TyG-BMI was found to correlate positively with future CHF.Additionally,introducing TyG-BMI into conventional prediction models resulted in a substantial improvement of their predictability for cardiovascular outcomes and overall mortality when compared to incorporating TyG or BMI alone.CONCLUSION Among T2DM individuals,a higher TyG-BMI is linked strongly to elevated risks of cardiovascular outcomes and overall mortality,highlighting its utility as a predictive marker for these risks.展开更多
The development of highly active and easily coupled non-noble metal electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is of great significance for the H_(2) production by water ele...The development of highly active and easily coupled non-noble metal electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is of great significance for the H_(2) production by water electrolysis.Here,we have shown an anion-modulated HER and OER activity of 1D Co-Mo based interstitial compound heterojunctions for effective overall water splitting.The Co-Mo based complex nanowires from a one-pot route with high yields can be converted into MoC-Co heterojunction nanowires under N_(2) atmosphere,while a pyrolysis under NH_(3) can give CoMoN-CoN heterostructures.The work function revealed Mott-Schottky effect between interfaces of two heterostructures,which can introduce electron redistribution and thus promote the HER/OER process.The MoC-Co heterojunction nanowires delivers good HER activity at a low overpotential of 39mV to afford a current density of 10mA/cm^(2).Density functional theory calculations show that the heterogeneous interface formed between the Co and MoC optimizes the hydrogen adsorption free energy.Concurrently,CoMoN-CoN heterojunction nanowires exhibits good OER performance with a low overpotential of 260mV to reach 10mA/cm^(2),being superior to RuO_(2).The two catalysts can be coupled to assemble a two-electrode cell with a solarto-hydrogen efficiency of 12.3%at 1.54 V.This work provides an effective means to design easily coupled HER and OER catalysts for H_(2) production by water electrolysis.展开更多
This study,a core-shell CoPt@C assembled hierarchical catalyst(named CoPt@C)was prepared using a unique CH_(4)deposition strategy for highly efficient overall water splitting.CoPt@C is composed of dense CoPt@C core-sh...This study,a core-shell CoPt@C assembled hierarchical catalyst(named CoPt@C)was prepared using a unique CH_(4)deposition strategy for highly efficient overall water splitting.CoPt@C is composed of dense CoPt@C core-shell nanoparticles(NPs)and a minor proportion of curled CoPt@nanotubes(CoPt@CNTs).Moreover,by adjusting the CH_(4)deposition time,the carbon shell thickness can be effectively regulated.Benefiting from the synergistic interaction between CoPt alloy and carbon shell,coupled with the high conductivity of the carbon shell,the overpotential of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)for CoPt@C is 15 and 120 mV at 10 mA cm^(-2).In addition,CoPt@C requires only 1.58 V to achieve 10 mA cm^(-2)for overall water splitting and maintains excellent stability over 80 h of continuous electrolysis.Density functional theory(DFT)calculations suggest that electrons transfer from the CoPt alloy NPs to the carbon shell,rendering the carbon shell electron-rich.Additionally,the hydrogen adsorption energy(ΔG*H)and the rate-determining step(ΔG*OOH)on CoPt@C are only-0.22 and 1.9 eV,respectively.展开更多
Given the limited exposure of active sites and the retarded separation of photogenerated charge carriers in those developed photocata-lysts,photocatalyticCO_(2)splitting into value-added chemicals has suffered from th...Given the limited exposure of active sites and the retarded separation of photogenerated charge carriers in those developed photocata-lysts,photocatalyticCO_(2)splitting into value-added chemicals has suffered from the poor activity and remained in great challenge for real application.Herein,hydrothermally synthesized BiOCl with layered structure(BOC-NSs)was exfoliated into thickness reduced nanosheets(BOCNSs-w)and even atomic layers(BOCNSs-i)via ultrasonication in water and isopro-panol,respectively.In comparison with the pristine BOCNSs,the exfoli-ated BiOCl,especially BOCNSs-i with atomically layered structure,exhibits much improved photocatalytic activity forCO_(2)overall splitting to produce CO andO_(2) at a stoichiometric ratio of 2:1,with CO evolution rate reaching 134.8µmolg^(-1)h^(-1) under simulated solar light(1.7 suns).By surpassing the photocatalytic performances of the state-of-the-artBi_(l)O_(m)X_(n)(X:Cl,Br,I)based photocatalysts,the CO evolution rate is further increased by 99 times,reaching 13.3 mmolg^(-1)h^(-1) under concentrated solar irradiation(34 suns).This excellent photocatalytic performance achieved over BOCNSs-i should be benefited from the shortened transfer distance and the increased built-in electric field intensity,which acceler-ates the migration of photogenerated charge carriers to surface.Moreover,with oxygen vacancies(VO)introduced into the atomic layers,BOCNSs-i is exposed with the electrons enriched Bi active sites that could transfer electrons to activateCO_(2)molecules for highly efficient and selective CO production,by lowering the energy barrier of rate-determining step(RDS),*OH+*CO_(2)-→HCO_(3)-.It is also realized that theH_(2)O vapor supplied during photocatalytic reaction would exchange oxygen atoms withCO_(2),which could alter the reaction path-ways and further reduce the energy barrier of RDS,contributing to the dramatically improved photocatalytic performance forCO_(2)overall splitting to CO andO_(2).展开更多
Designing the coordination environment of heteroatoms around metal sites and optimizing the electronic structure of diatomic metal sites remain significant challenges in achieving efficient CO_(2)overall splitting.Her...Designing the coordination environment of heteroatoms around metal sites and optimizing the electronic structure of diatomic metal sites remain significant challenges in achieving efficient CO_(2)overall splitting.Herein,we report four configurations(Cu/Ni-N_(4)C_(2),Cu/Ni-N_(2)C_(4),Cu/Ni-N_(2)C_(3)and Cu/Ni-N_(2)C_(2))constructed by precise regulation of the coordination environment around bimetallic atoms.Cu/Ni-N_(2)C_(2)showed high performance in electrochemical CO_(2)reduction(ECR)and water oxidation evolution reaction(OER).In the electrochemical CO_(2)overall splitting reaction,it achieved a Faraday efficiency of CO(FECO)of98.0%at a low cell voltage of-2.9 V,significantly higher than widely reported values.Moreover,the FE_(CO)is above 90%over-2.7 to-4.1 V of cell voltages.Cu/Ni-N_(2)C_(2)achieved long-term ECR stability of 110 h at-100 mA cm^(-2).Mechanism studies revealed that the change of coordination environment around the diatomic pairs moves the d-band center of the Ni atom closer to the Fermi level,thereby modulating the adsorption capacity of the catalysts to the reaction intermediates^(*)COOH and^(*)O.This work presents valuable insights into the rational design of diatomic catalysts and elucidates the intricate structureperformance relationship in advancing electrochemical CO_(2)overall splitting technology and energyconversion applications.展开更多
Developing bifunctional electrocatalysts with enhanced efficiency for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)remains a significant challenge.Herein,we constructed S-doped ultra-fine RuO...Developing bifunctional electrocatalysts with enhanced efficiency for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)remains a significant challenge.Herein,we constructed S-doped ultra-fine RuO_(2) nanodots that were uniformly dispersed on carbon nanotubes.The incorporation of S effectively induces local rearrangement of the electronic structure of RuO_(2),thereby enhancing the dispersion of RuO_(2) as active sites and optimizing the adsorption free energy of H^(∗)intermediate.As ex-pected,the as-synthesized S-RuO_(2)/CNT delivers remarkable HER activity in all pH electrolytes,achieving lower overpotentials of 136,159,and 396 mV at 100 mA cm^(-2) in acidic,neutral,and basic solutions,respectively.Moreover,a unitary S-RuO_(2)/CNT electrolytic cell requires only a lower voltage(1.476 V)to achieve a current density of 10 mA cm^(-2) in 1.0 mol/L KOH.This ingenious work represents a significant breakthrough in the rational design of bifunctional electrocatalysts,enabling remarkable performance in electrochemical water electrolysis.展开更多
基金supported by the National Natural Science Foundation of China(No.52274304).
文摘Designing a highly active and stable bifunctional catalyst is essential for achieving superior overall water splitting(OWS).In this study,a three-dimensional(3D)core-shell structure Co_(3)S_(4)/CuS@NiFe LDH nanocoral spheres electrocatalyst was constructed on nickel foam(NF)via an interfacial engineering strategy.This 3D core-shell heterostructure maximizes the exposure of active sites,optimizes the charge transport pathway and accelerates gas release rates.The protective shell strategy of NiFe LDH provides favorable stability,which contributes to inhibiting the electrochemical corrosion of the electrocatalyst and mitigating the toxic effects of Cl−and other microorganisms during the seawater splitting process.Moreover,the introduction of NiFe LDH induces a change in the OER mechanism from an adsorption evolution mechanism(AEM)to a lattice oxygen mechanism(LOM),which improves the intrinsic activity of the catalyst.Consequently,Co_(3)S_(4)/CuS@NiFe LDH demonstrates exceptional performance in the oxygen evolution reaction(OER)(η100=251 mV)and in the hydrogen evolution reaction(HER)(η100=254 mV),alongside remarkable stability over 100 h.For OWS,it exhibits a voltage of 1.46 V at 10 mA/cm^(2) and maintain stability for 100 h.Impressively,Co_(3)S_(4)/CuS@NiFe LDH still possesses outstanding activity and stability in natural alkaline seawater.This work proposes interfacial engineering to construct bifunctional catalysts with core-shell heterostructures,providing instructive guidelines for the design of highly efficient electrocatalysts toward seawater electrolysis.
基金Supported by the National Natural Science Foundation of China(No.52273056)the Science and Technology Development Program of Jilin Province,China(No.YDZJ202501ZYTS305)。
文摘Electrochemical water splitting represents a sustainable technology for hydrogen(H_(2))production.However,its large-scale implementation is hindered by the high overpotentials required for both the cathodic hydrogen evolution reaction(HER)and the anodic oxygen evolution reaction(OER).Transition metal-based catalysts have garnered significant research interest as promising alternatives to noble-metal catalysts,owing to their low cost,tunable composition,and noble-metal-like catalytic activity.Nevertheless,systematic reviews on their application as bifunctional catalysts for overall water splitting(OWS)are still limited.This review comprehensively outlines the principal categories of bifunctional transition metal electrocatalysts derived from electrospun nanofibers(NFs),including metals,oxides,phosphides,sulfides,and carbides.Key strategies for enhancing their catalytic performance are systematically summarized,such as heterointerface engineering,heteroatom doping,metal-nonmetal-metal bridging architectures,and single-atom site design.Finally,current challenges and future research directions are discussed,aiming to provide insightful perspectives for the rational design of high-performance electrocatalysts for OWS.
基金supported by the National Natural Science Foundation of China (No.22409038,52473221)Zhejiang Province Postdoctoral Science Foundation (No.ZJ2024021)+2 种基金Hubei Provincial Natural Science Foundation of China (Nos.2024DJC032,2025AFB889)Key Project of Science and Technology Research of Hubei Provincial Department of Education (Nos.D20232701,D20232702)the research grant funded by the Research,Development,and Innovation Authority (RDIA)-Kingdom of Saudi Arabia (No.12615-iu-2023-IU-R-2-1-EI-)。
文摘Hydrogen peroxide(H_(2)O_(2)) has been recognized as a green and nonpolluting multifunctional oxidant with extensive applications in environmental protection,metal etching,textile printing and dyeing,chemical synthesis and food processing.However,over 90 % of industrial H_(2)O_(2) is currently produced through the multi-step anthraquinone oxidation process,which suffers from a process with some drawbacks such as complex,high-energy consumption,and toxic byproducts emissions.Compared to the traditional anthraquinone method,artificial photosynthesis of H_(2)O_(2) using semiconductor photocatalysts has emerged as a sustainable alternative due to its use of water and O_(2) as the clean reactants and sole energy as the driving force.In recent years,metal-free photocatalysts mainly including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs) and carbon nitrile(g-C_(3)N_(4)) have garnered significant interest due to their superior thermal and chemical stability,diverse synthesis methods,tunable functionality,light weight nature and non-toxicity.These materials also exhibit adjustable band structure and unique photoelectric properties.Sustainable efforts have been made to advance metal-free photocatalysts for artificial photosynthesis of H_(2)O_(2),however,a comprehensive summary of current research status on metalfree-based photocatalytic overall H_(2)O_(2) production remain scarce.This review outlines recent process in overall H_(2)O_(2) photosynthesis based on metal-free photocatalysts.First,we introduced the fundamental concepts of photocatalytic overall H_(2)O_(2) production.Then,we analyze representative studies on photocatalytic overall H_(2)O_(2) synthesis using metal-free materials.Finally,we discuss the challenges and future perspectives in this field to guide the design and synthesis of metal-free systems for H_(2)O_(2) generation.
基金supported by the National Natural Science Foundation of China(Grant No.12375303)the Natural Science Foundation of Guangdong Province(Grants No.2024A1515030034 and 2023A1515140156).
文摘The design of efficient and cost‐effective bifunctional catalysts, which are capable of driving both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), is of paramount importance for advancing overall water splitting. Here, we developed an innovative heterogeneous interface engineering strategy to boost the electrocatalytic performance of overall water splitting. This approach involves the synergistic integration of ultra‐fine CoMoP nanocrystals coupled with three‐ dimensional (3D) porous C3N4/N‐doped carbon (NC) architectures, constructing a distinctive CoMoP/C3N4/NC heterogeneous interface. The CoMoP/C3N4/NC exhibits distinguished overall water splitting performance. To drive the overall water splitting current of 10 mA cm−2, the CoMoP/C3N4/NC||CoMoP/C3N4/NC electrolysis cell only needs an ultralow cell voltage of 1.496 V. The electronic properties and localized coordination environments characterizations, and density functional theory (DFT) calculations elucidate that the improved catalytic activities of CoMoP/C3N4/NC are primarily attributed to the synergistic interfacial coupling between CoMoP/C3N4/NC heterogeneous interface. A novel multi‐site synergistic catalytic mechanism was revealed by the DFT calculations, in which the optimum H* adsorption site on CoMoP/C3N4/NC for HER is on the cobalt atoms in CoMoP with the ultralow Gibbs free energy of hydrogen bonding (ΔGH*) of 0.018 eV, while for the OER, the optimum intermediates adsorption site of the CoMoP/C3N4/NC is on the carbon atoms in C3N4/NC. Besides, the intricately engineered 3D hierarchical porous framework of the CoMoP/C3N4/NC can facilitate the ion and electron transport and improve mass transfer, which gives rise to enhanced water splitting performance.
文摘BACKGROUND Esophageal carcinoma(EC)presents a significant public health issue in China,with its prognosis impacted by myriad factors.The creation of a reliable prog-nostic model for the overall survival(OS)of EC patients promises to greatly advance the customization of treatment approaches.AIM To create a more systematic and practical model that incorporates clinically significant indicators to support decision-making in clinical settings.METHODS This study utilized data from a prospective longitudinal cohort of 3127 EC patients treated at Chongqing University Cancer Hospital between January 1,2018,and December 12,2020.Utilizing the least absolute shrinkage and selection operator regression alongside multivariate Cox regression analyses helped pinpoint pertinent variables for constructing the model.Its efficacy was assessed by concordance index(C-index),area under the receiver operating characteristic curve(AUC),calibration curves,and decision curve analysis(DCA).RESULTS Nine variables were determined to be significant predictors of OS in EC patients:Body mass index(BMI),Karnofsky performance status,TNM stage,surgery,radiotherapy,chemotherapy,immunotherapy,platelet-to-lymphocyte ratio,and albumin-to-globulin ratio(ALB/GLB).The model demonstrated a C-index of 0.715(95%CI:0.701-0.729)in the training cohort and 0.711(95%CI:0.689-0.732)in the validation cohort.In the training cohort,AUCs for 1-year,3-year,and 5-year OS predictions were 0.773,0.787,and 0.750,respectively;in the validation cohort,they were 0.772,0.768,and 0.723,respectively,illustrating the model's precision.Calibration curves and DCA verified the model's predictive accuracy and net benefit.CONCLUSION A novel prognostic model for determining the OS of EC patients was successfully developed and validated to help clinicians in devising individualized treatment schemes for EC patients.
文摘BACKGROUND The prevalence and mortality rates of gastric carcinoma are disproportionately elevated in China,with the disease's intricate and varied characteristics further amplifying its health impact.Precise forecasting of overall survival(OS)is of paramount importance for the clinical management of individuals afflicted with this malignancy.AIM To develop and validate a nomogram model that provides precise gastric cancer prevention and treatment guidance and more accurate survival outcome prediction for patients with gastric carcinoma.METHODS Data analysis was conducted on samples collected from hospitalized gastric cancer patients between 2018 and 2020.Least absolute shrinkage and selection operator,univariate,and multivariate Cox regression analyses were employed to identify independent prognostic factors.A nomogram model was developed to predict gastric cancer patient outcomes.The model's predictability and discriminative ability were evaluated via receiver operating characteristic curves.To evaluate the clinical utility of the model,Kaplan-Meier and decision curve analyses were performed.RESULTS A total of ten independent prognostic factors were identified,including body mass index,tumor-node-metastasis(TNM)stage,radiation,chemotherapy,surgery,albumin,globulin,neutrophil count,lactate dehydrogenase,and platelet-to-lymphocyte ratio.The area under the curve(AUC)values for the 1-,3-,and 5-year survival prediction in the training set were 0.843,0.850,and 0.821,respectively.The AUC values were 0.864,0.820,and 0.786 for the 1-,3-,and 5-year survival prediction in the validation set,respectively.The model exhibited strong discriminative ability,with both the time AUC and time C-index exceeding 0.75.Compared with TNM staging,the model demonstrated superior clinical utility.Ultimately,a nomogram was developed via a web-based interface.CONCLUSION This study established and validated a novel nomogram model for predicting the OS of gastric cancer patients,which demonstrated strong predictive ability.Based on these findings,this model can aid clinicians in implementing personalized interventions for patients with gastric cancer.
基金supported by the Basic Science Center Program for Ordered Energy Conversion of the National Natural Science Foundation of China(No.52488201)the National Natural Science Foundation of China(No.52376209)+1 种基金the China Postdoctoral Science Foundation(Nos.2020T130503 and 2020M673386)China Fundamental Research Funds for the Central Universities.
文摘The development of stable and efficient non-noble metal cocatalysts has arisen as a promising yet challenging endeavor in the context of photocatalytic overall water splitting.In this study,NiCo alloy cocatalysts were synthesized with nickel/cobalt metal organic framework(NiCo-MOF)as source of nickel and cobalt.Systematic characterization results demonstrate the successful deposition of alloy cocatalysts onto the surface of SrTiO_(3).The prepared SrTiO_(3)loaded NiCo-alloy can generate hydrogen and oxygen in a stoichiometric ratio for photocatalytic overall water splitting,achieving an apparent quantum yield of 11.9%at 350±10 nm.Theoretical calculations indicate that the introduction of cobalt has a beneficial regulatory effect on the hydrogen evolution sites of Ni,reducing the free energy of H adsorption.The synergistic catalytic effect of bimetallic catalysts contributes to enhancing photocatalytic activity and stability.This study offers constructive insights for the development of high-efficiency and cost-effective cocatalyst systems.
文摘BACKGROUND Rectal cancer is prevalent and associated with substantial morbidity and mortality.AIM To develop a nomogram prediction model for overall survival(OS)in patients with rectal cancer by leveraging a comprehensive analysis of demographic,clinicopathological,haematological,and follow-up data to identify independent prognostic factors.METHODS We conducted a prospective cohort study in China involving rectal cancer patients and applied Cox regression and least absolute shrinkage and selection operator regression to assess the significance of various variables as independent prognostic factors for OS.The identified factors were integrated into a nomogram model,which was evaluated for predictive accuracy via the C-index,area under the curve(AUC),calibration curve,and decision curve analysis(DCA).RESULTS Multivariate analysis revealed independent predictors of OS,including the Karnofsky performance status,age,sex,TNM stage,chemotherapy,surgery,targeted therapy,β2-microglobulin,lactate dehydrogenase,and the neutrophil-to-lymphocyte ratio.The nomogram demonstrated a C-index of 0.80 for the training and validation cohorts,with AUC values indicating high predictive accuracy for 1-year,3-year,and 5-year OS.The calibration curves confirmed the model's excellent agreement with the observed survival rates,and DCA revealed the superior clinical utility of the nomogram over the TNM staging system.CONCLUSION In this study,a novel prognostic model that accurately predicts the OS of rectal cancer patients was developed.The model exhibited excellent discriminatory and calibration capabilities,thus offering a reliable tool for health care professionals to estimate patient survival.
基金supported by the National Natural Science Foundation of China(No.92741205)。
文摘Fixed-wing long-endurance aircraft play an important role in many fields.However,to reduce drag,these aircraft often have an enormous aspect ratio and wingspan,leading to challenges such as high requirements for takeoff and landing sites and poor wind resistance.Morphing may be able to solve this problem,but conventional morphing aircraft often employ complex actuation mechanisms and actuators to drive the morphing process.The associated costs in terms of structural weight increase and space occupancy are prohibitively high.First,this article develops a high-aspect-ratio aircraft with aerodynamic-driven morphing and validates the rationality and feasibility of this concept through flight tests.Then,focusing on the RQ-4‘‘Global Hawk”as the design baseline,the article explores multidisciplinary overall design methods for the aircraft,analyzing the comprehensive impact of morphing on aerodynamic,structural,and flight control design.Finally,the article elaborates on the benefits and costs associated with aerodynamic-driven morphing.
基金the financial support from National Natural Science Foundation of China (No. 21503097)Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. KYCX23_3905)。
文摘Metal-organic framework(MOF) has been widely applied in photocatalysis, which is significant for addressing energy crises and environmental issues. Based on density functional theory calculations,the performances of Cu-BTC, a copper-based MOF, and its derivatives Cu TM-BTC via the substitution of transition metal(TM) elements at the Cu site for photocatalytic overall water splitting(POWS) have been studied. POWS of Cu-BTC suffers from the sluggish hydrogen evolution reaction due to the large overpotential of 2.02 V and limited solar utilization due to a wide HOMO-LUMO gap of 4.11 e V. Via TM substitution, the HOMO-LUMO gap narrows but still satisfies the redox potentials when taken 3d-TM of Cr, Fe, Co or Ni, 4d-TM of Rh or Pd, or 5d-TM of Re or Pt into consideration, benefiting for the light absorption. Furthermore, Cr and Re could serve as active sites for hydrogen evolution with remarkably lowered overpotentials of 0.79 V and 0.28 V, respectively;similarly, oxygen evolution activities could be enhanced by Fe, Co and Rh because of their reduced overpotentials which are less than 0.5 V. Therefore,our findings pave guidance for designing Cu-BTC derivatives in overall water splitting.
基金the National Natural Science Foundation of China(Nos.52488201,52376209)the Fundamental Research Funds for the Central Universities.Zhenxiong Huang thanks the Key Project of Jiangxi Academy of Science(No.2022YYB05)the Science and Technology Innovation Project for Carbon Peak and Neutrality of Jiangxi Carbon Neutralization Research Center(2022JXST02).
文摘Solar-driven photocatalytic overall water splitting(POWS)has emerged as a sustainable pathway for hydrogen production,yet faces intrinsic challenges in developing robust catalysts that balance efficiency,stability,and cost-effectiveness.Polymeric carbon nitride(PCN)represents as a promising metal-free photocatalyst for hydrogen production due to the merits of unique electronic structure and exceptional thermal stability.Nevertheless,limited by rapid charge recombination and insufficient oxidative capability,little success has been achieved on pristine PCN photocatalyst in POWS.In this context,recent advances have demonstrated multi-dimensional modification strategies for improving POWS performance.Based on the fundamental principles of photocatalysis,this review discusses the advantages and challenges of PCN-based photocatalysts in POWS systems.With critical evaluation on one-step excitation systems and Z-scheme two-step excitation systems,modification strategies including crystallinity engineering,supramolecular precursor design,cocatalyst modulation,and construction of PCN-based heterojunctions and homojunctions were highlighted by introducing representative advances in POWS application over the past five years.Future perspectives for PCN-based photocatalysts are proposed,aiming to provide new insights for the design of advanced photocatalytic system for efficient POWS.
基金supported by the National Natural Science Foundation of China(Nos.22175060 and 22376062)JSPS Grant-in-Aid for Scientific Research(Nos.JP21H05235,JP22H05478 and JP22F22358)+1 种基金China Postdoctoral Science Foundation(No.2022M722867)the Key Research Project of Higher Education Institutions in Henan Province(No.23A530001).
文摘Exploring earth-abundant,highly active bifunctional electrocatalysts for efficient hydrogen and oxygen evolution is crucial for water splitting.However,due to their distinct free energies and conducting behaviors(electron/hole),balancing the catalytic efficiency between hydrogen and oxygen evolution remains challenging for achieving bifunctional electrocatalysts.Here,we report a locally-doped MoS_(2)monolayer with an in-plane heterostructure acting as a bifunctional electrocatalyst and apply it to the overall water splitting.In this heterostructure,the core region contains Mo/S vacancies,while the ring region was doped by Fe atoms(in two substitution configurations:1FeMo and 3FeMo-VS clusters)with a p-type conductive characteristic.Our micro-cell measurements,combined with density functional theory(DFT)calculations,reveal that the vacancies-rich core region presents remarkable hydrogen evolution reaction(HER)activity while the Fe-doped ring gives an excellent oxygen evolution reaction(OER)activity,thus forming an in-plane bifunctional electrocatalyst.Finally,as a proof-of-concept for overall water splitting,we constructed a full-cell configuration based on a locally-doped MoS_(2)monolayer,which achieved a cell voltage of 1.87 V at 10 mA·cm^(-2),demonstrating outstanding performance in strong acid electrolytes.Our work provides insight into the hetero-integration of bifunctional electrocatalysts at the atomic level,paving the way for designing transition metal dichalcogenide catalysts with activity-manipulated regions capable of multiple reactions.
基金supported by the National Natural Science Foundation of China(Nos.52302272 and 52377026)the Taishan Scholars Program(Nos.tsqn202211124 and tsqn202103057)+4 种基金the Natural Science Foundation of Shandong Province(Nos.ZR2022QB023 and ZR2024ME046)the Qingchuang Talents Induction Program of Shandong Higher Education Insti-tution(Research and Innovation Team of Marine Polysaccharides Fibers-based Energy Materials)the Key Innovative Research Team of New Energy Materials and Devices(No.BBXYKYTDxjZD01)the University Natural Science Research Project of Anhui Province(No.2022AH010101)the State Key Laboratory of Bio-Fibers and Eco-Textiles,Qingdao University(Nos.ZKT10 and GZRC202006).
文摘Anion exchange membrane electrolysis (AEMWE) is currently a promising technology to produce hydrogen from water. Developing the highly intrinsic activity of electrodes is extremely important. In this paper, nitrogen vacancies-rich cobalt nitride (Co_(4)N-VN) is used as the anode catalyst of the urea oxidation reaction (UOR) and its loading Pt (Pt@Co_(4)N-VN) acted as the cathode of hydrogen evolution reaction (HER). The introduction of N-vacancies gained the electron-deficient Co_(4)N more favorable for the UOR process. Meanwhile, the electron transfer between the Co_(4)N-VN carrier and Pt can enhance the intrinsic HER activity of loaded Pt. Specifically, in the 0.33 M urea and 1.0 M KOH electrolyte, the UOR potential of CO_(4)N-VN is only 1.58 V at the current density of 300.0 mA cm^(-2), which is much lower than that of Co_(4) N and Co_(3)O_(4). At the same time, the HER overpotential at 1.0 M KOH and 300.0 mA cm^(-2) is only 120.0 mV, lower than 20 wt% Pt/C. By measuring the bode phase diagram, the presence of N-vacancies can accelerate the electron transfer rate of catalysts to improve the UOR and HER electrocatalytic activity. The overall water-splitting device featuring Pt@Co_(4)N-VN||Co_(4)N-VN electrodes achieves a voltage of 2.99 V at a current density of 300.0 mA cm^(-2).
基金financially supported by National Natural Science Foundation of China(No.52473327,51572295,21273285 and 21003157)National Key R&D Program of China(No.2021YFA1501300,2019YFC1907602).
文摘Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination,yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear.Herein,density functional theory(DFT)calculations first reveal the modulation of sulfur vacancy concentrations on Co_(9)S_(8)electronic structures,predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting.Experimentally fabricated Co_(9)S_(8)with appropriate sulfur vacancies exhibits superior bifunctional activity(HER:164 mV@_(η10);OER:297 mV@_(η100)).The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V(10 mA cm^(−2))for over 60 h.Experimental studies illustrate that sulfur vacancies preferentially adsorb OH^(−)during reactions,inducing the formation of CoOOH active phases.DFT analysis further indicates that OH^(−)adsorption weakens d-p orbital hybridization,optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance.This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics,electronic structures and catalytic performance.
文摘BACKGROUND Although recent studies have reported the reliability of triglyceride-glucose index(TyG)as a biomarker for evaluation of insulin resistance,the research exploring the association of TyG-body mass index(BMI)with major cardiovascular outcomes and all-cause mortality among the type 2 diabetes mellitus(T2DM)population remains scarce.AIM To ascertain whether TyG-BMI correlates with cardiovascular outcomes and mortality risk in individuals diagnosed with T2DM.METHODS Data were drawn from the ACCORD trial and its subsequent follow-up(ACCORDION),which together included 10190 participants.To evaluate the associations of TyG-BMI with future cardiovascular outcomes and overall mortality risk among T2DM patients,Cox’s proportional-hazards model was employed.Non-linear associations and thresholds were investigated by performing restricted cubic spline regression,fitting smooth curves,and conducting piecewise regression.Additionally,we examined whether the above findings were robust through interaction and subgroup analyses.The robustness of results was further verified by a series of sensitivity assessments.Through the area under the receiver operating characteristic curve estimation,the incremental predictive power of TyG-BMI beyond conventional risk factors was also evaluated.RESULTS Applying multivariable Cox regression analysis,we identified a significant correlation of TyG-BMI with both cardiovascular outcomes and overall mortality.Specifically,after adjusting for multiple confounders,the cardiovascular mortality,congestive heart failure(CHF)and overall mortality risks in the highest TyG-BMI quartile were 1.74,2.65 and 1.42 times greater,respectively,when compared to the lowest quartile.The analysis revealed that TyG-BMI was linked nonlinearly to both types of mortality,while a two-stage linear regression discerned inflection points at 252.77 for cardiovascular mortality and 245.90 for overall mortality.TyG-BMI was found to correlate positively with future CHF.Additionally,introducing TyG-BMI into conventional prediction models resulted in a substantial improvement of their predictability for cardiovascular outcomes and overall mortality when compared to incorporating TyG or BMI alone.CONCLUSION Among T2DM individuals,a higher TyG-BMI is linked strongly to elevated risks of cardiovascular outcomes and overall mortality,highlighting its utility as a predictive marker for these risks.
基金support of this research by the National Natural Science Foundation of China(No.91961111)the Natural Science Foundation of Heilongjiang Province(No.ZD2021B003)Fundamental Research Funds for the Central Universities(No.2572022BU05).
文摘The development of highly active and easily coupled non-noble metal electrocatalysts for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)is of great significance for the H_(2) production by water electrolysis.Here,we have shown an anion-modulated HER and OER activity of 1D Co-Mo based interstitial compound heterojunctions for effective overall water splitting.The Co-Mo based complex nanowires from a one-pot route with high yields can be converted into MoC-Co heterojunction nanowires under N_(2) atmosphere,while a pyrolysis under NH_(3) can give CoMoN-CoN heterostructures.The work function revealed Mott-Schottky effect between interfaces of two heterostructures,which can introduce electron redistribution and thus promote the HER/OER process.The MoC-Co heterojunction nanowires delivers good HER activity at a low overpotential of 39mV to afford a current density of 10mA/cm^(2).Density functional theory calculations show that the heterogeneous interface formed between the Co and MoC optimizes the hydrogen adsorption free energy.Concurrently,CoMoN-CoN heterojunction nanowires exhibits good OER performance with a low overpotential of 260mV to reach 10mA/cm^(2),being superior to RuO_(2).The two catalysts can be coupled to assemble a two-electrode cell with a solarto-hydrogen efficiency of 12.3%at 1.54 V.This work provides an effective means to design easily coupled HER and OER catalysts for H_(2) production by water electrolysis.
基金financially supported by the Natural Science Foundation of National(No.NSFC22208179)the Key Laboratory of Laser Technology and Optoelectronic Functional Materials of Hainan Province(No.2024LTOM05)
文摘This study,a core-shell CoPt@C assembled hierarchical catalyst(named CoPt@C)was prepared using a unique CH_(4)deposition strategy for highly efficient overall water splitting.CoPt@C is composed of dense CoPt@C core-shell nanoparticles(NPs)and a minor proportion of curled CoPt@nanotubes(CoPt@CNTs).Moreover,by adjusting the CH_(4)deposition time,the carbon shell thickness can be effectively regulated.Benefiting from the synergistic interaction between CoPt alloy and carbon shell,coupled with the high conductivity of the carbon shell,the overpotential of hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)for CoPt@C is 15 and 120 mV at 10 mA cm^(-2).In addition,CoPt@C requires only 1.58 V to achieve 10 mA cm^(-2)for overall water splitting and maintains excellent stability over 80 h of continuous electrolysis.Density functional theory(DFT)calculations suggest that electrons transfer from the CoPt alloy NPs to the carbon shell,rendering the carbon shell electron-rich.Additionally,the hydrogen adsorption energy(ΔG*H)and the rate-determining step(ΔG*OOH)on CoPt@C are only-0.22 and 1.9 eV,respectively.
基金the financial support from the National Key R&D Program of China(2024YFF0506100)the National Natural Science Foundation of China(52225606 and 52488201).
文摘Given the limited exposure of active sites and the retarded separation of photogenerated charge carriers in those developed photocata-lysts,photocatalyticCO_(2)splitting into value-added chemicals has suffered from the poor activity and remained in great challenge for real application.Herein,hydrothermally synthesized BiOCl with layered structure(BOC-NSs)was exfoliated into thickness reduced nanosheets(BOCNSs-w)and even atomic layers(BOCNSs-i)via ultrasonication in water and isopro-panol,respectively.In comparison with the pristine BOCNSs,the exfoli-ated BiOCl,especially BOCNSs-i with atomically layered structure,exhibits much improved photocatalytic activity forCO_(2)overall splitting to produce CO andO_(2) at a stoichiometric ratio of 2:1,with CO evolution rate reaching 134.8µmolg^(-1)h^(-1) under simulated solar light(1.7 suns).By surpassing the photocatalytic performances of the state-of-the-artBi_(l)O_(m)X_(n)(X:Cl,Br,I)based photocatalysts,the CO evolution rate is further increased by 99 times,reaching 13.3 mmolg^(-1)h^(-1) under concentrated solar irradiation(34 suns).This excellent photocatalytic performance achieved over BOCNSs-i should be benefited from the shortened transfer distance and the increased built-in electric field intensity,which acceler-ates the migration of photogenerated charge carriers to surface.Moreover,with oxygen vacancies(VO)introduced into the atomic layers,BOCNSs-i is exposed with the electrons enriched Bi active sites that could transfer electrons to activateCO_(2)molecules for highly efficient and selective CO production,by lowering the energy barrier of rate-determining step(RDS),*OH+*CO_(2)-→HCO_(3)-.It is also realized that theH_(2)O vapor supplied during photocatalytic reaction would exchange oxygen atoms withCO_(2),which could alter the reaction path-ways and further reduce the energy barrier of RDS,contributing to the dramatically improved photocatalytic performance forCO_(2)overall splitting to CO andO_(2).
基金supported by Shanxi Provincial Key Research and Development Project(No.20201102002)。
文摘Designing the coordination environment of heteroatoms around metal sites and optimizing the electronic structure of diatomic metal sites remain significant challenges in achieving efficient CO_(2)overall splitting.Herein,we report four configurations(Cu/Ni-N_(4)C_(2),Cu/Ni-N_(2)C_(4),Cu/Ni-N_(2)C_(3)and Cu/Ni-N_(2)C_(2))constructed by precise regulation of the coordination environment around bimetallic atoms.Cu/Ni-N_(2)C_(2)showed high performance in electrochemical CO_(2)reduction(ECR)and water oxidation evolution reaction(OER).In the electrochemical CO_(2)overall splitting reaction,it achieved a Faraday efficiency of CO(FECO)of98.0%at a low cell voltage of-2.9 V,significantly higher than widely reported values.Moreover,the FE_(CO)is above 90%over-2.7 to-4.1 V of cell voltages.Cu/Ni-N_(2)C_(2)achieved long-term ECR stability of 110 h at-100 mA cm^(-2).Mechanism studies revealed that the change of coordination environment around the diatomic pairs moves the d-band center of the Ni atom closer to the Fermi level,thereby modulating the adsorption capacity of the catalysts to the reaction intermediates^(*)COOH and^(*)O.This work presents valuable insights into the rational design of diatomic catalysts and elucidates the intricate structureperformance relationship in advancing electrochemical CO_(2)overall splitting technology and energyconversion applications.
基金financially supported by the Joint Fund of Science and Technology R&D Plan of Henan Province(No.232301420003)。
文摘Developing bifunctional electrocatalysts with enhanced efficiency for both hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)remains a significant challenge.Herein,we constructed S-doped ultra-fine RuO_(2) nanodots that were uniformly dispersed on carbon nanotubes.The incorporation of S effectively induces local rearrangement of the electronic structure of RuO_(2),thereby enhancing the dispersion of RuO_(2) as active sites and optimizing the adsorption free energy of H^(∗)intermediate.As ex-pected,the as-synthesized S-RuO_(2)/CNT delivers remarkable HER activity in all pH electrolytes,achieving lower overpotentials of 136,159,and 396 mV at 100 mA cm^(-2) in acidic,neutral,and basic solutions,respectively.Moreover,a unitary S-RuO_(2)/CNT electrolytic cell requires only a lower voltage(1.476 V)to achieve a current density of 10 mA cm^(-2) in 1.0 mol/L KOH.This ingenious work represents a significant breakthrough in the rational design of bifunctional electrocatalysts,enabling remarkable performance in electrochemical water electrolysis.
