CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed gra...CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.展开更多
CO_(2) photoreduction into carbon-based chemicals has been considered as an appropriate way to alleviate the energy issue and greenhouse effect.Herein,the 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt(II)(CoTCPP)h...CO_(2) photoreduction into carbon-based chemicals has been considered as an appropriate way to alleviate the energy issue and greenhouse effect.Herein,the 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt(II)(CoTCPP)has been integrated with BiOBr microspheres and formed the CoTCPP/BiOBr composite.The as-prepared CoTCPP/BiOBr-2 composite shows optimized photocatalytic performance for CO_(2) conversion into CO and CH_(4) upon irradiation with 300 W Xe lamp,which is 2.03 and 2.58 times compared to that of BiOBr,respectively.The introduced CoTCPP significantly enhanced light absorption properties,promoted rapid separation of photogenerated carriers and boosted the chemisorption of CO_(2) molecules.The metal Co^(2+) at the center of the porphyrin molecules also acts as adsorption center for CO_(2) molecules,accelerating the CO_(2) conversion into CO and CH_(4).The possible mechanism of CO_(2) photoreduction was explored by in-situ FT-IR spectra.This work offers a new possibility for the preparation of advanced photocatalysts.展开更多
High-performance perovskite photodetectors with self-driven characteristic usually need electron/hole transport layers to extract carriers. However, these devices with transport layer structure are prone to result in ...High-performance perovskite photodetectors with self-driven characteristic usually need electron/hole transport layers to extract carriers. However, these devices with transport layer structure are prone to result in a poor perovskite/transport layer interface, which restricts the performance and stability of the device. To solve this problem, this work reports a novel device structure in which perovskite nanowires are in-situ prepared on PbI_(2), which serves as both a reaction raw material and efficient carrier extraction layer. By optimizing the thickness of PbI_(2), nanowire growth time, and ion exchange time, a selfdriven photodetector with an ITO/PbI_(2)/CsPbBr_(3)/carbon structure is constructed. The optimized device achieves excellent performance with the responsivity of 0.33 A/W, the detectivity of as high as 3.52 × 10^(13) Jones. Furthermore, the device can detect the light with its optical power lowered to 0.1 nW/cm^(2). This research provides a new method for preparing perovskite nano/micro devices with simple structure but excellent performance.展开更多
Hydrogen peroxide(H_(2)O_(2)),as an essential and green chemical,is extensively used in energy and environmental applications.However,the production of H_(2)O_(2)primarily relies on the anthraquinone method,which is a...Hydrogen peroxide(H_(2)O_(2)),as an essential and green chemical,is extensively used in energy and environmental applications.However,the production of H_(2)O_(2)primarily relies on the anthraquinone method,which is an energy-intensive method involving multi-step reactions,producing harmful by-product wastes.Solar-driven H_(2)O_(2)production,an alternative route for H_(2)O_(2)generation,is a green and sustainable technology since it only utilizes water and oxygen as feedstock.However,the rapid recombination of charge carriers as well as insufficient redox capability limit the photocatalytic H_(2)O_(2)production performance.Constructing step-scheme(S-scheme)heterojunction photocatalysts has been regarded as an effective strategy to address these drawbacks because it not only achieves spatially separated charge carriers,but also preserves redox capability of the photocatalytic system.This paper covers the recent advances of S-scheme heterojunction photocatalysts for H_(2)O_(2)production in terms of basic principles,characterization techniques,and preparation strategies.Moreover,the mechanism and advantages of S-scheme heterojunction for photocatalytic H_(2)O_(2)generation are systematically discussed.The recent S-scheme heterojunction designs,including inorganic-organic heterojunction,inorganic-inorganic heterojunction,and organic-organic heterojunction,are summarized.Lastly,the challenges and research directions of S-scheme photocatalysts for H_(2)O_(2)generation are presented.展开更多
High-entropy alloy(HEA)offer tunable composition and surface structures,enabling the creation of novel active sites that enhance catalytic performance in renewable energy application.However,the inherent surface compl...High-entropy alloy(HEA)offer tunable composition and surface structures,enabling the creation of novel active sites that enhance catalytic performance in renewable energy application.However,the inherent surface complexity and tendency for elemental segregation,which results in discrepancies between bulk and surface compositions,pose challenges for direct investigation via density functional theory.To address this,Monte Carlo simulations combined with molecular dynamics were employed to model surface segregation across a broad range of elements,including Cu,Ag,Au,Pt,Pd,and Al.The analysis revealed a trend in surface segregation propensity following the order Ag>Au>Al>Cu>Pd>Pt.To capture the correlation between surface site characteristics and the free energy of multi-dentate CO_(2)reduction intermediates,a graph neural network was designed,where adsorbates were transformed into pseudo-atoms at their centers of mass.This model achieved mean absolute errors of 0.08–0.15 eV for the free energies of C_(2)intermediates,enabling precise site activity quantification.Results indicated that increasing the concentration of Cu,Ag,and Al significantly boosts activity for CO and C_(2)formation,whereas Au,Pd,and Pt exhibit negative effects.By screening stable composition space,promising HEA bulk compositions for CO,HCOOH,and C_(2)products were predicted,offering superior catalytic activity compared to pure Cu catalysts.展开更多
Storing solar energy in battery systems is crucial to achieving a green and sustainable society.However,the efficient development of photo-enhanced zinc-air batteries(ZABs)is limited by the rapid recombination of phot...Storing solar energy in battery systems is crucial to achieving a green and sustainable society.However,the efficient development of photo-enhanced zinc-air batteries(ZABs)is limited by the rapid recombination of photogenerated carriers on the photocathode.In this work,the visible-light-driven CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst with unique petal-like layer structure was designed and developed,which can be used as air electrode for visible-light-driven ZABs.The superior performance of ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)was mainly attributed to the successful construction of Schottky heterojunction between g-C_(3)N_(4)and carbon nanotubes(CNTs),which accelerates the transfer of electrons from g-C_(3)N_(4)to CoS_(2)/CuS cocatalysts,improves the carrier separation ability,and extends the carrier lifetime.Thereinto,the visible-driven ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst has a power density of 588.90 mW cm^(-2) and a charge-discharge cycle of 643 h under visible light irradiation,which is the highest performance ever reported for photo-enhanced ZABs.More importantly,the charge-discharge voltage drop of ZABs was only 0.54 V under visible light irradiation,which is significantly lower than the voltage drop(0.94 V)in the dark.This study provides a new idea for designing efficient and stable visible-light-driven ZABs cathode catalysts.展开更多
BACKGROUND Pancreatic cancer,characterized by aggressive proliferation and metastasis,is a lethal malignancy.The nightly hormone melatonin serves as a rhythm-regulating hormone,and is used to treat different cancers i...BACKGROUND Pancreatic cancer,characterized by aggressive proliferation and metastasis,is a lethal malignancy.The nightly hormone melatonin serves as a rhythm-regulating hormone,and is used to treat different cancers including pancreatic cancer.AIM To investigate how melatonin acts against human pancreatic cancer cell lines and analyze the biological processes that cause the observed effects.METHODS Panc-1 and AsPC-1 cells were treated with melatonin.Cell viability was measured using the cell counting kit-8 assay.Western blotting and immunofluorescence were used to analyze protein expression levels.Ferroptosis was measured by analyzing lipid reactive oxygen species and malondialdehyde levels;apoptosis was assessed using flow cytometry.RESULTS Melatonin significantly inhibited the viability,colony formation,migration,and invasion of Panc-1 and AsPC-1 cells.Additionally,melatonin activated the endoplasmic reticulum(ER)stress pathway(protein kinase R-like ER kinase eukaryotic initiation factor 2α-activating transcription factor 4),inhibited glutamine metabolism(alanine-serinecysteine transporter 2-glutaminase 1-glutathione peroxidase 4,alanine-serine-cysteine transporter 2-glutathione peroxidase 4),and promoted ferroptosis in pancreatic cancer cells.Co-treatment with a high melatonin concentration and protein kinase R-like ER kinase agonist(CCT020312)enhanced melatonin-induced ferroptosis in pancreatic cancer cells.Melatonin demonstrated a variety of anticancer effects by inhibiting autophagy.This was achieved through the increased expression of sequestosome-1 and decreased expression of light chain 3.Additionally,melatonin facilitated the promotion of apoptosis.CONCLUSION Melatonin induces ferroptosis in pancreatic cancer cells by activating transcription factor 4-dependent ER stress and inhibiting glutamine metabolism,promotes apoptosis in pancreatic cancer cells,and inhibits autophagy,leading to synergistic anticancer effects.展开更多
Disulfidptosis,a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis(TMS),has showed tremendous potential in cancer therapy.However,the efficacy of disulfidptosis is limited by...Disulfidptosis,a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis(TMS),has showed tremendous potential in cancer therapy.However,the efficacy of disulfidptosis is limited by poor permeability of drugs in solid tumors.Herein,hydrogen sulfide(H_(2)S)and nearinfrared(NIR)light-driven nanomotors(denoted as HGPP)have been constructed to efficiently penetrate tumors and induce disulfidptosis.HGPP demonstrate glutathione(GSH)-responsive release of H_(2)S,which combined with NIR light-induced photothermal effect drive HGPP movement to facilitate deep tumor penetration.The released H_(2)S induces tumor acidosis and disrupts TMS,where disulfide accumulation following cell starvation leads to disulfidptosis.In addition,HGPP induce hepatoma specific cellular uptake and catalyze the conversion of glucose and oxygen to produce hydrogen peroxide(H_(2)O_(2)),leading to glucose starvation.Overall,this study has developed a multifunctional Janus nanomotor that provides a novel strategy for disulfidptosis-based solid tumor therapy.展开更多
Organic-inorganic hybrid perovskite solar cells achieve remarkable efficiencies(>26%)yet face stability challenges.Quasi-2D alternating-cation-interlayer perovskites offer enhanced stability through hydrophobic spa...Organic-inorganic hybrid perovskite solar cells achieve remarkable efficiencies(>26%)yet face stability challenges.Quasi-2D alternating-cation-interlayer perovskites offer enhanced stability through hydrophobic spacer cations but suffer from vertical phase segregation and buried interface defects.Herein,we introduce dicyanodiamide(DCD)to simultaneously address these dual limitations in GA(MA)_(n)Pb_(n)I_(3n+1)perovskites.The guanidine group in DCD passivates undercoordinated Pb^(2+)and MA^(+)vacancies at the perovskite/TiO_(2)interface,while cyano groups eliminate oxygen vacancies in TiO_(2)via Ti^(4+)-CN coordination,reducing interfacial trap density by 73%with respect to the control sample.In addition,DCD regulates crystallization kinetics,suppressing low-n-phase aggregation and promoting vertical alignment of high-n phases,which benefit for carrier transport.This dual-functional modification enhances charge transport and stabilizes energy-level alignment.The optimized devices achieve a record power conversion efficiency of 21.54%(vs.19.05%control)and retain 94%initial efficiency after 1200 h,outperforming unmodified counterparts(84%retention).Combining defect passivation with phase homogenization,this work establishes a molecular bridge strategy to decouple stability-efficiency trade-offs in low-dimensional perovskites,providing a universal framework for interface engineering in high-performance optoelectronics.展开更多
The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy...The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO_(2)/UiO-66-NH_(2)hybrid material with abundant oxygen vacancies,enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde.By optimizing the solvothermal treatment duration,the composite(UiO-66-NH_(2)-2h)achieves a 74.1%conversion of benzyl alcohol with>99%selectivity toward benzaldehyde under mild conditions,substantially out-performing pristine UiO-66-NH_(2).Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall,uniformly dispersed ZrO_(2)nanoparticles(~2.3 nm)within the MOF matrix,while simultaneously generating abundant oxygen vacancies,as confirmed by XPS,EPR,and HRTEM analyses.The defect-mediated electronic structure of the ZrO_(2)/UiO-66-NH_(2)hybrid enhances visible-light absorption,facilitates charge carrier separation,and pro-motes efficient activation of O_(2)into superoxide radicals(·O_(2)^(−)),the primary reactive species.Transient photocurrent measure-ments and electrochemical impedance spectroscopy further verify the improved charge separation efficiency.The synergistic interplay between oxygen vacancies and the intimate ZrO_(2)/UiO-66-NH_(2)interface provides a unique defect-mediated charge transfer pathway,distinguishing this system from conventional heterojunctions.This study demonstrates a facile,one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts,off ering a scalable route for solar-driven organic synthesis.展开更多
Exploration of efficient and stable photocatalysts to mimic natural leaves for the conversion of atmospheric CO_(2)into hydrocarbons utilizing solar light is very important but remains a major challenge.Herein,we repo...Exploration of efficient and stable photocatalysts to mimic natural leaves for the conversion of atmospheric CO_(2)into hydrocarbons utilizing solar light is very important but remains a major challenge.Herein,we report the design of four novel metal-salen-incorporated conjugated microporous polymers as robust artificial leaves for photoreduction of atmospheric CO_(2)with gaseous water.Owing to the rich nitrogen and oxygen moieties in the polymeric frameworks,they show a maximum CO_(2)adsorption capacity of 46.1 cm3 g^(−1)and adsorption selectivity for CO_(2)/N_(2)of up to 82 at 273 K.Under air atmosphere and simulated solar light(100mWcm^(−2)),TEPT-Zn shows an excellent CO yield of 304.96μmol h^(−1)g^(−1)with a selectivity of approximately 100%,which represents one of the best results in terms of organic photocatalysts for gas-phase CO_(2)photoreduction so far.Furthermore,only small degradation in the CO yield is observed even after 120-h continuous illumination.More importantly,a good CO yield of 152.52μmol g^(−1)was achieved by directly exposing the photocatalytic reaction of TEPT-Zn in an outdoor environment for 3 h(25-28℃,52.3±7.9mWcm^(−2)).This work provides an avenue for the continued development of advanced polymers toward gas-phase photoconversion of CO_(2)from air.展开更多
CO_(2)-free H_(2)refers to H_(2)production process without CO_(2)emission,which is a promising clean energy in the future.Catalytic decomposition of methane(CDM)is a competitive technology to produce CO_(2)-free H2 wi...CO_(2)-free H_(2)refers to H_(2)production process without CO_(2)emission,which is a promising clean energy in the future.Catalytic decomposition of methane(CDM)is a competitive technology to produce CO_(2)-free H2 with large-scale.However,CDM reaction is highly endothermic and is kinetically and thermodynamically unfavorable,which typically requires a harsh reaction temperature above 800℃.In this work,solar-driven photothermal catalytic decomposition of methane was firstly introduced to produce CO_(2)-free H_(2)relying solely on solar energy as the driving force.A high H_(2)yield of 204.6 mmol g^(–1)h^(–1)was observed over Ni-CeO2 interface under photothermal conditions,along with above 87%reduction in the apparent activation energy(11.2 vs.87.3 kJ mol^(–1))when comparing with the traditional thermal catalysis.Further studies suggested that Ni/CeO_(2)catalyst enhanced optical absorption in visible-infrared region to ensure the heat energy for methane decomposition.The generated electrons and holes participated in the redox process of photo-driven CDM reaction with enhanced separation ability of hot carriers excited by ultraviolet-visible light,which lowered activation energy and improved the photothermal catalytic activity.This work provides a promising photothermal catalytic strategy to produce CO_(2)-free H^(2)under mild conditions.展开更多
Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy convers...Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.展开更多
Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenv...Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenvironments.Herein,we synthesize CeO_(2)with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag_(2)O nanoparticles(Ag_(2)O/Vo-CeO_(2)).Vo-CeO_(2)acts as a multifunctional modulator,regulating both the reaction microenvironment and the electronic structure of Ag sites,thereby boosting CO_(2)reduction(CO_(2)RR)efficiency.Its strong CO_(2)adsorption and H_(2)O dissociation capabilities facilitate the supply of CO_(2)and active^(*)H species to Ag sites.The electron-withdrawing effect of VoCeO_(2)induces polarization at interfacial Ag sites,generating Agd+species that enhance CO_(2)affinity and activation.Moreover,the electronic coupling between Vo-CeO_(2)and Ag upshifts the d-band center of Ag,optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step.Ag_(2)O/Vo-CeO_(2)delivers a consistently high Faraday efficiency(FE)of over 99% for CO production even at industrially current density(up to 365 mA cm^(-2)herein),and the operational potential window spans an astonishing 1700 m V(FE>95%).The unprecedented activity,which overcomes the trade-off between the selectivity and current density for CO_(2)RR,outperforms state-of-the-art Ag-based catalysts reported to date.These findings offer a promising pathway to develop robust CO_(2)RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation.展开更多
The zinc indium sulfide(ZnIn_(2)S_(4))semiconductors have garnered significant interest in photocatalysis due to their environmentally friendly characteristics,appropriate bandgap,and high absorption coefficient.Howev...The zinc indium sulfide(ZnIn_(2)S_(4))semiconductors have garnered significant interest in photocatalysis due to their environmentally friendly characteristics,appropriate bandgap,and high absorption coefficient.However,the exploration of advanced strategies to realize the effective and tailored doping still poses significant challenges in enhancing hydrogen evolution performance.In this work,a mild cation exchange strategy is reported to incorporate Ag cations into flower-like ZnIn_(2)S_(4) microspheres,enabling the selective replacement of Zn atoms by Ag.Remarkably,the as-fabricated Ag-ZnIn_(2)S_(4) exhibited exceptional photocatalytic hydrogen production performance,achieving a rate of 8098μmol·g^(−1)·h^(−1) under visible light irradiation.This is 4 times than that of pristine ZnIn_(2)S_(4)(2002μmol·g^(−1)·h^(−1)),and stands as the highest one among metal-doped-ZnIn_(2)S_(4) photocatalysts ever reported.Along with the theoretical calculations,it has been confirmed that the enhanced photocatalytic hydrogen generation behavior can primarily be attributed to the synergistic effect with improved light absorption,reduced adsorption energy,increased active sites and optimized charge carrier transfer,induced by the cation exchange with Ag in ZnIn_(2)S_(4).This work might provide some valuable insights on the design and development of highly efficient visible light driven photocatalysts for water splitting applications.展开更多
As an extreme physical condition,high pressure serves as a potent means to substantially modify the interatomic distances and bonding patterns within condensed matter,thereby enabling the macroscopic manipulation of m...As an extreme physical condition,high pressure serves as a potent means to substantially modify the interatomic distances and bonding patterns within condensed matter,thereby enabling the macroscopic manipulation of material properties.We employed the CALYPSO method to predict the stable structures of RbB_(2)C_(4)across the pressure range from 0 GPa to 100 GPa and investigated its physical properties through first-principles calculations.Specially,we found four novel structures,namely,P6_(3)/mcm-,Amm2-,P1-,and I4/mmm-RbB_(2)C_(4).Under pressure conditions,electronic structure calculations reveal that all of them exhibit metallic characteristics.The calculation results of formation enthalpy show that the P6_(3)/mcm structure can be synthesized within the pressure range of 0–40 GPa.Specially,the Amm2,P1,and I4/mmm structures can be synthesized above 4 GPa,6 GPa,10 GPa,respectively.Moreover,the estimated Vickers hardness value of I4/mmm-RbB_(2)C_(4)compound is 47 GPa,suggesting that it is a superhard material.Interestingly,this study uncovers the continuous transformation of the crystal structure of RbB_(2)C_(4)from a layered configuration to folded and tubular forms,ultimately attaining a stabilized cage-like structure under the pressure span of 0–100 GPa.The application of pressure offers a formidable impetus for the advancement and innovation in condensed matter physics,facilitating the exploration of novel states and functions of matter.展开更多
Built-in electric field coupled piezoelectric polarization engineering is a promising method to adjust and boost the catalytic performance of photocatalysts.Herein,BiOIO_(3)-Bi_(2)Te_(3) type-II heterojunction piezo-p...Built-in electric field coupled piezoelectric polarization engineering is a promising method to adjust and boost the catalytic performance of photocatalysts.Herein,BiOIO_(3)-Bi_(2)Te_(3) type-II heterojunction piezo-photocatalyst was proposed and prepared by a sequential hydro-solvothermal method.Due to the co-drive of the heterojunction and photothermal-piezoelectric polarization effect certified by piezoelectric force microscopy,COMSOL simulations,and infrared thermography,the photocatalytic degradation performance of the as-prepared BiOIO_(3)-Bi_(2)Te_(3) on rhodamine B was dramatically improved under the co-excitation of visible light and ultrasound compared with under the single light irradiation and the single ultrasonic conditions.Typically,the BiOIO_(3)-Bi_(2)Te_(3) photocatalyst always showed significantly better catalytic degradation performance than the pure Bi_(2)Te_(3),BiOIO_(3),and BiOIO_(3)/Bi_(2)Te_(3) mechanical mixtures.Impressively,based on the optimal conditions obtained by systematically studying the effects of temperatures,ultrasound intensities,and inorganic salts on the piezo-photocatalytic rhodamine B degradation,the optimum composite ratio BiOIO_(3)-Bi_(2)Te_(3)-20 piezo-photocatalyst can also effectively remove tetracycline and Cr(VI),and also achieve the purpose of simultaneously removing a mixture of these three pollutants with good recycling stability.Such enhanced catalytic performance was mainly attributed to the disruptions of the electrostatic equilibrium and saturation effects of the built-in electric field under successive ultrasonic and photoinduced co-disturbance,thus enhancing the driving force of separation and migration of photogenerated carriers as verified by electrochemical tests,energy band structure theory,and DFT calculations.Based on which and the sacrificial agent experiments,the photocatalytic degradation mechanism was proposed.This research showcased the significant potential for environmental remediation using solar energy and mechanical energy cooperatively.展开更多
Lithium-carbon dioxide(Li-CO_(2))batteries using high ion-conductive inorganic molten salt electrolytes have recently attracted much attention due to the high energy density and potential application of carbon neutral...Lithium-carbon dioxide(Li-CO_(2))batteries using high ion-conductive inorganic molten salt electrolytes have recently attracted much attention due to the high energy density and potential application of carbon neutrality.However,the poor Li-ion conductivity of the molten-salt electrolytes at room temperature(RT)makes these batteries lose most of their capacity and power as the temperature falls below 80℃.Here,inspired by the greenhouse effect,we report an RT molten salt Li-CO_(2)battery where solar energy can be efficiently harvested and converted into heat that is further localized on the cathode consisting of plasmonic ruthenium(Ru)catalysts and Li_(2)CO_(3)-based products via a greenhouse-like phenomenon.As a result,the solar-driven molten salt Li-CO_(2)battery demonstrates a larger full discharge/charge capacity of 9.5 mA h/8.1 mA h,and a longer cycle lifespan of 250 cycles at 500 mA/g with a limited capacity of 500 mA h/g at RT than the molten salt Li-CO_(2)battery at 130℃.Notably,the average temperature of the cathode increases by 8℃ after discharge to 0.75 mA h,which indicates the infrared radiation from Ru catalysts can be effectively suppressed by discharged Li_(2)CO_(3)-based products.This battery technology paves the way for developing low-temperature molten salt energy storage devices.展开更多
Ce-β-Bi_(2)O_(3)/AgI was prepared using solvothermal calcination and in-situ deposition methods.The introduction of Ce can inhibit the conversion of Bi_(2)O_(3)fromβtoαphase at high temperatures,promoting the forma...Ce-β-Bi_(2)O_(3)/AgI was prepared using solvothermal calcination and in-situ deposition methods.The introduction of Ce can inhibit the conversion of Bi_(2)O_(3)fromβtoαphase at high temperatures,promoting the formation of oxygen vacancies(OVs)in the photocatalyst.OVs can adsorb more dissolved oxygen to promote the formation rate of·O^(-)_(2).Moreover,the interaction between Ce-Bi_(2)O_(3)and AgI results in the formation of Z-scheme heterojunctions,which can broaden the light absorption region,facilitate photogenerated carrier separation and transfer and enhance the ability to produce more active oxygen species(ROS).The morphology,crystal,element distribution and photo-electric chemical properties of the Ce-Bi_(2)O_(3)/AgI were analyzed,and the result shows that the optimal ratio of Ce-Bi_(2)O_(3)/AgI photocatalyst achieves a removal rate of 88.63%(180 min)of tetracycline(TC)(20 mg/L)and 100%(120 min)of methyl orange(MO)(20 mg/L).This work clarified the photocatalytic degradation mechanism,providing a promising avenue for developing photocatalytic composites by rare earth metal doping in environme ntal remediation applications.展开更多
Subsurface rocks,as complex porous media,exhibit multiscale pore structures and intricate physical properties.Digital rock physics technology has become increasingly influential in the study of subsurface rock propert...Subsurface rocks,as complex porous media,exhibit multiscale pore structures and intricate physical properties.Digital rock physics technology has become increasingly influential in the study of subsurface rock properties.Given the multiscale characteristics of rock pore structures,direct three-dimensional imaging at sub-micrometer and nanometer scales is typically infeasible.This study introduces a method for reconstructing porous media using multidimensional data,which combines one-dimensional pore structure parameters with two-dimensional images to reconstruct three-dimensional models.The pore network model(PNM)is stochastically reconstructed using one-dimensional parameters,and a generative adversarial network(GAN)is utilized to equip the PNM with pore morphologies derived from two-dimensional images.The digital rocks generated by this method possess excellent controllability.Using Berea sandstone and Grosmont carbonate samples,we performed digital rock reconstructions based on PNM extracted by the maximum ball algorithm and compared them with stochastically reconstructed PNM.Pore structure parameters,permeability,and formation factors were calculated.The results show that the generated samples exhibit good consistency with real samples in terms of pore morphology,pore structure,and physical properties.Furthermore,our method effectively supplements the micropores not captured in CT images,demonstrating its potential in multiscale carbonate samples.Thus,the proposed reconstruction method is promising for advancing porous media property research.展开更多
文摘CeO_(2) based semiconductor are widely used in solar-driven photothermal catalytic dry reforming of methane(DRM)reaction,but still suffer from low activity and low light utilization efficiency.This study developed graphite-CeO_(2) interfaces to enhance solar-driven photothermal catalytic DRM.Compared with carbon nanotubes-modified CeO_(2)(CeO_(2)-CNT),graphite-modified CeO_(2)(CeO_(2)-GRA)constructed graphite-CeO_(2) interfaces with distortion in CeO_(2),leading to the formation abundant oxygen vacancies.These graphite-CeO_(2) interfaces with oxygen vacancies enhanced optical absorption and promoted the generation and separation of photogenerated carriers.The high endothermic capacity of graphite elevated the catalyst surface temperature from 592.1−691.3℃,boosting light-to-thermal conversion.The synergy between photogenerated carriers and localized heat enabled Ni/CeO_(2)-GRA to achieve a CO production rate of 9985.6 mmol/(g·h)(vs 7192.4 mmol/(g·h)for Ni/CeO_(2))and a light-to-fuel efficiency of 21.8%(vs 13.8%for Ni/CeO_(2)).This work provides insights for designing graphite-semiconductor interfaces to advance photothermal catalytic efficiency.
基金financially supported by National Natural Science Foundation of China(Nos.22138011,22108106 and 22108108)China Postdoctoral Science Foundation(Nos.2022M721380 and 2020M680065)Hong Kong Scholar Program(XJ2021021).
文摘CO_(2) photoreduction into carbon-based chemicals has been considered as an appropriate way to alleviate the energy issue and greenhouse effect.Herein,the 5,10,15,20-tetra(4-carboxyphenyl)porphyrin cobalt(II)(CoTCPP)has been integrated with BiOBr microspheres and formed the CoTCPP/BiOBr composite.The as-prepared CoTCPP/BiOBr-2 composite shows optimized photocatalytic performance for CO_(2) conversion into CO and CH_(4) upon irradiation with 300 W Xe lamp,which is 2.03 and 2.58 times compared to that of BiOBr,respectively.The introduced CoTCPP significantly enhanced light absorption properties,promoted rapid separation of photogenerated carriers and boosted the chemisorption of CO_(2) molecules.The metal Co^(2+) at the center of the porphyrin molecules also acts as adsorption center for CO_(2) molecules,accelerating the CO_(2) conversion into CO and CH_(4).The possible mechanism of CO_(2) photoreduction was explored by in-situ FT-IR spectra.This work offers a new possibility for the preparation of advanced photocatalysts.
基金financially supported by the National Natural Science Foundation of China (51972101)the Research platforms and projects of Guangdong Universities in 2022 (2022ZDZX1028)Guangdong Provincial Key Laboratory Project (2023KSYS003)。
文摘High-performance perovskite photodetectors with self-driven characteristic usually need electron/hole transport layers to extract carriers. However, these devices with transport layer structure are prone to result in a poor perovskite/transport layer interface, which restricts the performance and stability of the device. To solve this problem, this work reports a novel device structure in which perovskite nanowires are in-situ prepared on PbI_(2), which serves as both a reaction raw material and efficient carrier extraction layer. By optimizing the thickness of PbI_(2), nanowire growth time, and ion exchange time, a selfdriven photodetector with an ITO/PbI_(2)/CsPbBr_(3)/carbon structure is constructed. The optimized device achieves excellent performance with the responsivity of 0.33 A/W, the detectivity of as high as 3.52 × 10^(13) Jones. Furthermore, the device can detect the light with its optical power lowered to 0.1 nW/cm^(2). This research provides a new method for preparing perovskite nano/micro devices with simple structure but excellent performance.
文摘Hydrogen peroxide(H_(2)O_(2)),as an essential and green chemical,is extensively used in energy and environmental applications.However,the production of H_(2)O_(2)primarily relies on the anthraquinone method,which is an energy-intensive method involving multi-step reactions,producing harmful by-product wastes.Solar-driven H_(2)O_(2)production,an alternative route for H_(2)O_(2)generation,is a green and sustainable technology since it only utilizes water and oxygen as feedstock.However,the rapid recombination of charge carriers as well as insufficient redox capability limit the photocatalytic H_(2)O_(2)production performance.Constructing step-scheme(S-scheme)heterojunction photocatalysts has been regarded as an effective strategy to address these drawbacks because it not only achieves spatially separated charge carriers,but also preserves redox capability of the photocatalytic system.This paper covers the recent advances of S-scheme heterojunction photocatalysts for H_(2)O_(2)production in terms of basic principles,characterization techniques,and preparation strategies.Moreover,the mechanism and advantages of S-scheme heterojunction for photocatalytic H_(2)O_(2)generation are systematically discussed.The recent S-scheme heterojunction designs,including inorganic-organic heterojunction,inorganic-inorganic heterojunction,and organic-organic heterojunction,are summarized.Lastly,the challenges and research directions of S-scheme photocatalysts for H_(2)O_(2)generation are presented.
文摘High-entropy alloy(HEA)offer tunable composition and surface structures,enabling the creation of novel active sites that enhance catalytic performance in renewable energy application.However,the inherent surface complexity and tendency for elemental segregation,which results in discrepancies between bulk and surface compositions,pose challenges for direct investigation via density functional theory.To address this,Monte Carlo simulations combined with molecular dynamics were employed to model surface segregation across a broad range of elements,including Cu,Ag,Au,Pt,Pd,and Al.The analysis revealed a trend in surface segregation propensity following the order Ag>Au>Al>Cu>Pd>Pt.To capture the correlation between surface site characteristics and the free energy of multi-dentate CO_(2)reduction intermediates,a graph neural network was designed,where adsorbates were transformed into pseudo-atoms at their centers of mass.This model achieved mean absolute errors of 0.08–0.15 eV for the free energies of C_(2)intermediates,enabling precise site activity quantification.Results indicated that increasing the concentration of Cu,Ag,and Al significantly boosts activity for CO and C_(2)formation,whereas Au,Pd,and Pt exhibit negative effects.By screening stable composition space,promising HEA bulk compositions for CO,HCOOH,and C_(2)products were predicted,offering superior catalytic activity compared to pure Cu catalysts.
文摘Storing solar energy in battery systems is crucial to achieving a green and sustainable society.However,the efficient development of photo-enhanced zinc-air batteries(ZABs)is limited by the rapid recombination of photogenerated carriers on the photocathode.In this work,the visible-light-driven CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst with unique petal-like layer structure was designed and developed,which can be used as air electrode for visible-light-driven ZABs.The superior performance of ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)was mainly attributed to the successful construction of Schottky heterojunction between g-C_(3)N_(4)and carbon nanotubes(CNTs),which accelerates the transfer of electrons from g-C_(3)N_(4)to CoS_(2)/CuS cocatalysts,improves the carrier separation ability,and extends the carrier lifetime.Thereinto,the visible-driven ZABs assembled by CoS_(2)/CuS@CNT-C_(3)N_(4)photocatalyst has a power density of 588.90 mW cm^(-2) and a charge-discharge cycle of 643 h under visible light irradiation,which is the highest performance ever reported for photo-enhanced ZABs.More importantly,the charge-discharge voltage drop of ZABs was only 0.54 V under visible light irradiation,which is significantly lower than the voltage drop(0.94 V)in the dark.This study provides a new idea for designing efficient and stable visible-light-driven ZABs cathode catalysts.
基金Supported by Jinhua Municipal Science and Technology Bureau,No.2022-4-254.
文摘BACKGROUND Pancreatic cancer,characterized by aggressive proliferation and metastasis,is a lethal malignancy.The nightly hormone melatonin serves as a rhythm-regulating hormone,and is used to treat different cancers including pancreatic cancer.AIM To investigate how melatonin acts against human pancreatic cancer cell lines and analyze the biological processes that cause the observed effects.METHODS Panc-1 and AsPC-1 cells were treated with melatonin.Cell viability was measured using the cell counting kit-8 assay.Western blotting and immunofluorescence were used to analyze protein expression levels.Ferroptosis was measured by analyzing lipid reactive oxygen species and malondialdehyde levels;apoptosis was assessed using flow cytometry.RESULTS Melatonin significantly inhibited the viability,colony formation,migration,and invasion of Panc-1 and AsPC-1 cells.Additionally,melatonin activated the endoplasmic reticulum(ER)stress pathway(protein kinase R-like ER kinase eukaryotic initiation factor 2α-activating transcription factor 4),inhibited glutamine metabolism(alanine-serinecysteine transporter 2-glutaminase 1-glutathione peroxidase 4,alanine-serine-cysteine transporter 2-glutathione peroxidase 4),and promoted ferroptosis in pancreatic cancer cells.Co-treatment with a high melatonin concentration and protein kinase R-like ER kinase agonist(CCT020312)enhanced melatonin-induced ferroptosis in pancreatic cancer cells.Melatonin demonstrated a variety of anticancer effects by inhibiting autophagy.This was achieved through the increased expression of sequestosome-1 and decreased expression of light chain 3.Additionally,melatonin facilitated the promotion of apoptosis.CONCLUSION Melatonin induces ferroptosis in pancreatic cancer cells by activating transcription factor 4-dependent ER stress and inhibiting glutamine metabolism,promotes apoptosis in pancreatic cancer cells,and inhibits autophagy,leading to synergistic anticancer effects.
基金supported by the National Natural Science Foundation of China(No.22171230)the Project of Science and Technology of Social Development in Shaanxi Province(Nos.2024SF-YBXM-294,2023-YBSF-151)。
文摘Disulfidptosis,a novel mechanism of programmed cell death through the disruption of tumor metabolic symbiosis(TMS),has showed tremendous potential in cancer therapy.However,the efficacy of disulfidptosis is limited by poor permeability of drugs in solid tumors.Herein,hydrogen sulfide(H_(2)S)and nearinfrared(NIR)light-driven nanomotors(denoted as HGPP)have been constructed to efficiently penetrate tumors and induce disulfidptosis.HGPP demonstrate glutathione(GSH)-responsive release of H_(2)S,which combined with NIR light-induced photothermal effect drive HGPP movement to facilitate deep tumor penetration.The released H_(2)S induces tumor acidosis and disrupts TMS,where disulfide accumulation following cell starvation leads to disulfidptosis.In addition,HGPP induce hepatoma specific cellular uptake and catalyze the conversion of glucose and oxygen to produce hydrogen peroxide(H_(2)O_(2)),leading to glucose starvation.Overall,this study has developed a multifunctional Janus nanomotor that provides a novel strategy for disulfidptosis-based solid tumor therapy.
基金support from the National Key R&D Program of China(Grant No.2023YFE0111500)the National Natural Science Foundation of China(Grant No.52321006,T2394480,T2394484,22109143,22479131)+8 种基金Beijing National Laboratory for Molecular Sciences(BNLMS-CXXM-202005)the China Postdoctoral Innovative Talent Support Program(Grant No.BX2021271)the China Postdoctoral Science Foundation(2022M712851)the Opening Project of State Key Laboratory of Advanced Technology for Float Glass(Grant No.2022KF04)Graduate Education Reform Project of Henan Province(Grant No.2023SJGLX136Y)Key R&D Special Program of Henan Province(Grant No.241111242000)Program for Science and Technology Innovation Talents in Universities of Henan Province(Grant No.25HASTIT005)Training Plan for Young Backbone Teachers of Zhengzhou University(Grant No.2023ZDGGJS017)the Joint Research Project of Puyang Shengtong Juyuan New Materials Co.,Ltd.(Grant No.20230128A).
文摘Organic-inorganic hybrid perovskite solar cells achieve remarkable efficiencies(>26%)yet face stability challenges.Quasi-2D alternating-cation-interlayer perovskites offer enhanced stability through hydrophobic spacer cations but suffer from vertical phase segregation and buried interface defects.Herein,we introduce dicyanodiamide(DCD)to simultaneously address these dual limitations in GA(MA)_(n)Pb_(n)I_(3n+1)perovskites.The guanidine group in DCD passivates undercoordinated Pb^(2+)and MA^(+)vacancies at the perovskite/TiO_(2)interface,while cyano groups eliminate oxygen vacancies in TiO_(2)via Ti^(4+)-CN coordination,reducing interfacial trap density by 73%with respect to the control sample.In addition,DCD regulates crystallization kinetics,suppressing low-n-phase aggregation and promoting vertical alignment of high-n phases,which benefit for carrier transport.This dual-functional modification enhances charge transport and stabilizes energy-level alignment.The optimized devices achieve a record power conversion efficiency of 21.54%(vs.19.05%control)and retain 94%initial efficiency after 1200 h,outperforming unmodified counterparts(84%retention).Combining defect passivation with phase homogenization,this work establishes a molecular bridge strategy to decouple stability-efficiency trade-offs in low-dimensional perovskites,providing a universal framework for interface engineering in high-performance optoelectronics.
基金the National Natural Sci-ence Foundation of China(Nos.22271038,22378038,22172012)C.P.thanks Dalian Science and Technology Innovation Fund(No.2024JJ12CG033)+1 种基金C.P.and Z.S thank State Key Laboratory of Heavy Oil Processing(Nos.WX20230149,SKLHOP202402005)Y.-Y.L.thanks the Guangxi Key Laboratory of Information Materials,Guilin University of Electronic Technology(No.231019-K).
文摘The development of efficient photocatalysts for selective organic transformations under visible light remains a major challenge in sustainable chemistry.In this study,we present a straightforward solvothermal strategy for fabricating a defect-engineered ZrO_(2)/UiO-66-NH_(2)hybrid material with abundant oxygen vacancies,enabling the visible-light-driven oxidation of benzyl alcohol to benzaldehyde.By optimizing the solvothermal treatment duration,the composite(UiO-66-NH_(2)-2h)achieves a 74.1%conversion of benzyl alcohol with>99%selectivity toward benzaldehyde under mild conditions,substantially out-performing pristine UiO-66-NH_(2).Structural and mechanistic studies reveal that the solvothermal process induces the in situ formation of ultrasmall,uniformly dispersed ZrO_(2)nanoparticles(~2.3 nm)within the MOF matrix,while simultaneously generating abundant oxygen vacancies,as confirmed by XPS,EPR,and HRTEM analyses.The defect-mediated electronic structure of the ZrO_(2)/UiO-66-NH_(2)hybrid enhances visible-light absorption,facilitates charge carrier separation,and pro-motes efficient activation of O_(2)into superoxide radicals(·O_(2)^(−)),the primary reactive species.Transient photocurrent measure-ments and electrochemical impedance spectroscopy further verify the improved charge separation efficiency.The synergistic interplay between oxygen vacancies and the intimate ZrO_(2)/UiO-66-NH_(2)interface provides a unique defect-mediated charge transfer pathway,distinguishing this system from conventional heterojunctions.This study demonstrates a facile,one-step approach to integrate defect engineering with interfacial hybridization in MOF-based photocatalysts,off ering a scalable route for solar-driven organic synthesis.
基金Research Foundation for Advanced Talents of East China University of Technology,Grant/Award Number:DHBK201927Excellent Youth Foundation of Jiangxi Scientific Committee,Grant/Award Number:20232ACB213012+2 种基金National Science Foundation for Young Scientists of China,Grant/Award Number:21905122National Science Foundation for Young Scientists,Grant/Award Number:21905147Jiangxi Talent Program,Grant/Award Number:DHSQT32022005.
文摘Exploration of efficient and stable photocatalysts to mimic natural leaves for the conversion of atmospheric CO_(2)into hydrocarbons utilizing solar light is very important but remains a major challenge.Herein,we report the design of four novel metal-salen-incorporated conjugated microporous polymers as robust artificial leaves for photoreduction of atmospheric CO_(2)with gaseous water.Owing to the rich nitrogen and oxygen moieties in the polymeric frameworks,they show a maximum CO_(2)adsorption capacity of 46.1 cm3 g^(−1)and adsorption selectivity for CO_(2)/N_(2)of up to 82 at 273 K.Under air atmosphere and simulated solar light(100mWcm^(−2)),TEPT-Zn shows an excellent CO yield of 304.96μmol h^(−1)g^(−1)with a selectivity of approximately 100%,which represents one of the best results in terms of organic photocatalysts for gas-phase CO_(2)photoreduction so far.Furthermore,only small degradation in the CO yield is observed even after 120-h continuous illumination.More importantly,a good CO yield of 152.52μmol g^(−1)was achieved by directly exposing the photocatalytic reaction of TEPT-Zn in an outdoor environment for 3 h(25-28℃,52.3±7.9mWcm^(−2)).This work provides an avenue for the continued development of advanced polymers toward gas-phase photoconversion of CO_(2)from air.
文摘CO_(2)-free H_(2)refers to H_(2)production process without CO_(2)emission,which is a promising clean energy in the future.Catalytic decomposition of methane(CDM)is a competitive technology to produce CO_(2)-free H2 with large-scale.However,CDM reaction is highly endothermic and is kinetically and thermodynamically unfavorable,which typically requires a harsh reaction temperature above 800℃.In this work,solar-driven photothermal catalytic decomposition of methane was firstly introduced to produce CO_(2)-free H_(2)relying solely on solar energy as the driving force.A high H_(2)yield of 204.6 mmol g^(–1)h^(–1)was observed over Ni-CeO2 interface under photothermal conditions,along with above 87%reduction in the apparent activation energy(11.2 vs.87.3 kJ mol^(–1))when comparing with the traditional thermal catalysis.Further studies suggested that Ni/CeO_(2)catalyst enhanced optical absorption in visible-infrared region to ensure the heat energy for methane decomposition.The generated electrons and holes participated in the redox process of photo-driven CDM reaction with enhanced separation ability of hot carriers excited by ultraviolet-visible light,which lowered activation energy and improved the photothermal catalytic activity.This work provides a promising photothermal catalytic strategy to produce CO_(2)-free H^(2)under mild conditions.
文摘Photoredox dual reaction of organic synthesis and H2 evolution opens up a novel pathway for collaboratively generating clean fuels and high-quality chemicals,providing a more effective approach of solar energy conversion.Herein,a surface defect-engineered ZnCoS/ZnCdS heterostructure with zinc blende(ZB)/wurtzite(WZ)phase junctions is synthesized for photocatalytic cooperative coupling of benzaldehyde(BAD)and H_(2) production.This surface defect-engineered ZnCoS/ZnCdS heterostructure elaborately integrates the mixed phase junction advantage of ZnCdS semiconductor and the cocatalytic function of ZnCoS possessing Zn(VZn-ZnCoS/ZnCdS)or S vacancies(VS-ZnCoS/ZnCdS).The optimum VS-ZnCoS/ZnCdS simultaneously exhibits a superior H2 production rate of 14.23 mmol h^(-1) g^(-1) accompanied with BAD formation rate of 12.29 mmol h^(-1) g^(-1) under visible-light irradiation,which is approximately two-fold greater than that of pristine ZnCdS.Under simulated sunlight irradiation(AM 1.5),VS-ZnCoS/ZnCdS achieves H2 evolution(27.43 mmol gcat^(-1) h^(-1))with 0.52%of STH efficiency,accompany with 26.31 mmol gcat^(-1) h^(-1) of BAD formation rate.The underlying solar-driven mechanism is elucidated by a series of in-situ characterization and control experiments,which reveals the synergistic effect of interfacial ZB/WZ phase junctions in ZnCdS and S vacancies of ZnCoS on enhancement of the photoredox dual reaction.The VS-ZnCoS/ZnCdS follows a predominant oxygen-centered radical integrating with carbon-centered radical pathways for BAD formation and a simultaneous electron-driven proton reduction for H_(2) production.Interestingly,the nature of surface vacancies not only facilitates the separation of photoinduced charge carriers but also able to selectively adjust the mechanism pathway for BAD production via tuning the oxygen-centered radical and carbon-centered radical formation.
基金the support of this research by the Nat ional Natural Science Foundation of China(22179035)the Hei-longjiang Provincial Natural Science Foundation Joint Fund Cultivation Project(PL2024B012)the Fundamental Research Funds for the Universities of Heilongjiang Province(2023-KYYWF-1440)。
文摘Although the potential of microenvironment modulation to enhance electricity-driven CO_(2)reduction has been recognized,substantial challenges remain,particularly in effectively integrating multiple favorable microenvironments.Herein,we synthesize CeO_(2)with abundant oxygen vacancies to effectively disperse and anchor small-sized Ag_(2)O nanoparticles(Ag_(2)O/Vo-CeO_(2)).Vo-CeO_(2)acts as a multifunctional modulator,regulating both the reaction microenvironment and the electronic structure of Ag sites,thereby boosting CO_(2)reduction(CO_(2)RR)efficiency.Its strong CO_(2)adsorption and H_(2)O dissociation capabilities facilitate the supply of CO_(2)and active^(*)H species to Ag sites.The electron-withdrawing effect of VoCeO_(2)induces polarization at interfacial Ag sites,generating Agd+species that enhance CO_(2)affinity and activation.Moreover,the electronic coupling between Vo-CeO_(2)and Ag upshifts the d-band center of Ag,optimizing COOH binding and lowering the thermodynamic barrier of the potential-determining step.Ag_(2)O/Vo-CeO_(2)delivers a consistently high Faraday efficiency(FE)of over 99% for CO production even at industrially current density(up to 365 mA cm^(-2)herein),and the operational potential window spans an astonishing 1700 m V(FE>95%).The unprecedented activity,which overcomes the trade-off between the selectivity and current density for CO_(2)RR,outperforms state-of-the-art Ag-based catalysts reported to date.These findings offer a promising pathway to develop robust CO_(2)RR catalysts and present an engineering strategy for constructing the optimal microenvironment of active sites via the synergistic effects of multifunctional modulation.
基金supported by the National Natural Science Foundation of China(Nos.52272085 and 52372063)Zhejiang Provincial Natural Science Foundation of China(No.LY23E020002)+1 种基金Ningbo Youth Science and Technology Innovation Leading Talents Project(No.2023QL031)the Postdoctoral Fellowship Program of CPSF(No.GZC20233006).
文摘The zinc indium sulfide(ZnIn_(2)S_(4))semiconductors have garnered significant interest in photocatalysis due to their environmentally friendly characteristics,appropriate bandgap,and high absorption coefficient.However,the exploration of advanced strategies to realize the effective and tailored doping still poses significant challenges in enhancing hydrogen evolution performance.In this work,a mild cation exchange strategy is reported to incorporate Ag cations into flower-like ZnIn_(2)S_(4) microspheres,enabling the selective replacement of Zn atoms by Ag.Remarkably,the as-fabricated Ag-ZnIn_(2)S_(4) exhibited exceptional photocatalytic hydrogen production performance,achieving a rate of 8098μmol·g^(−1)·h^(−1) under visible light irradiation.This is 4 times than that of pristine ZnIn_(2)S_(4)(2002μmol·g^(−1)·h^(−1)),and stands as the highest one among metal-doped-ZnIn_(2)S_(4) photocatalysts ever reported.Along with the theoretical calculations,it has been confirmed that the enhanced photocatalytic hydrogen generation behavior can primarily be attributed to the synergistic effect with improved light absorption,reduced adsorption energy,increased active sites and optimized charge carrier transfer,induced by the cation exchange with Ag in ZnIn_(2)S_(4).This work might provide some valuable insights on the design and development of highly efficient visible light driven photocatalysts for water splitting applications.
基金Project supported by the Jilin Provincial Science and Technology Development Joint Fund Project(Grant No.YDZJ202201ZYTS581)supported by the Scientific and Technological Research Project of Jilin Provincial Education Department(Grant No.JJKH20240077KJ).
文摘As an extreme physical condition,high pressure serves as a potent means to substantially modify the interatomic distances and bonding patterns within condensed matter,thereby enabling the macroscopic manipulation of material properties.We employed the CALYPSO method to predict the stable structures of RbB_(2)C_(4)across the pressure range from 0 GPa to 100 GPa and investigated its physical properties through first-principles calculations.Specially,we found four novel structures,namely,P6_(3)/mcm-,Amm2-,P1-,and I4/mmm-RbB_(2)C_(4).Under pressure conditions,electronic structure calculations reveal that all of them exhibit metallic characteristics.The calculation results of formation enthalpy show that the P6_(3)/mcm structure can be synthesized within the pressure range of 0–40 GPa.Specially,the Amm2,P1,and I4/mmm structures can be synthesized above 4 GPa,6 GPa,10 GPa,respectively.Moreover,the estimated Vickers hardness value of I4/mmm-RbB_(2)C_(4)compound is 47 GPa,suggesting that it is a superhard material.Interestingly,this study uncovers the continuous transformation of the crystal structure of RbB_(2)C_(4)from a layered configuration to folded and tubular forms,ultimately attaining a stabilized cage-like structure under the pressure span of 0–100 GPa.The application of pressure offers a formidable impetus for the advancement and innovation in condensed matter physics,facilitating the exploration of novel states and functions of matter.
基金funded by the Natural Science Foundation of Jilin Province of China(No.20240101075JC)Henan Province Science and Technology programs(No.242102230096)+3 种基金the National Natural Science Foundation of China(52372174)the Science and Technology Research key Project of the Education Department of Henan Province(No.24A430049)the Carbon Neutrality Research Institute Fund(CNIF20230204)the Special Project of Strategic Cooperation between China National Petroleum Corporation and China University of Petroleum(Beijing)(ZLZX-2020-04).
文摘Built-in electric field coupled piezoelectric polarization engineering is a promising method to adjust and boost the catalytic performance of photocatalysts.Herein,BiOIO_(3)-Bi_(2)Te_(3) type-II heterojunction piezo-photocatalyst was proposed and prepared by a sequential hydro-solvothermal method.Due to the co-drive of the heterojunction and photothermal-piezoelectric polarization effect certified by piezoelectric force microscopy,COMSOL simulations,and infrared thermography,the photocatalytic degradation performance of the as-prepared BiOIO_(3)-Bi_(2)Te_(3) on rhodamine B was dramatically improved under the co-excitation of visible light and ultrasound compared with under the single light irradiation and the single ultrasonic conditions.Typically,the BiOIO_(3)-Bi_(2)Te_(3) photocatalyst always showed significantly better catalytic degradation performance than the pure Bi_(2)Te_(3),BiOIO_(3),and BiOIO_(3)/Bi_(2)Te_(3) mechanical mixtures.Impressively,based on the optimal conditions obtained by systematically studying the effects of temperatures,ultrasound intensities,and inorganic salts on the piezo-photocatalytic rhodamine B degradation,the optimum composite ratio BiOIO_(3)-Bi_(2)Te_(3)-20 piezo-photocatalyst can also effectively remove tetracycline and Cr(VI),and also achieve the purpose of simultaneously removing a mixture of these three pollutants with good recycling stability.Such enhanced catalytic performance was mainly attributed to the disruptions of the electrostatic equilibrium and saturation effects of the built-in electric field under successive ultrasonic and photoinduced co-disturbance,thus enhancing the driving force of separation and migration of photogenerated carriers as verified by electrochemical tests,energy band structure theory,and DFT calculations.Based on which and the sacrificial agent experiments,the photocatalytic degradation mechanism was proposed.This research showcased the significant potential for environmental remediation using solar energy and mechanical energy cooperatively.
基金supported by the National Natural Science Foundation of China(NSFC,62104099,61921005,62105048,62204117 and 62073299)the Science and Technology Research Program of Chongqing Education Commission(KJQN202100633)+5 种基金the Postdoctoral Science Foundation of China(2021M693768 and 2021M701057)the Key Scientific Research Project in Colleges and Universities of Henan Province,China(21A416001)the Key Laboratory for Special Functional Materials(KEKT2022-06)the Natural Science Foundation of Jiangsu Province(BK20210275 and BK20230498)the support from Jiangsu Province Science Foundation for Youths(BK20210275)National Natural Science Foundation of China(NSFC,62204117)。
文摘Lithium-carbon dioxide(Li-CO_(2))batteries using high ion-conductive inorganic molten salt electrolytes have recently attracted much attention due to the high energy density and potential application of carbon neutrality.However,the poor Li-ion conductivity of the molten-salt electrolytes at room temperature(RT)makes these batteries lose most of their capacity and power as the temperature falls below 80℃.Here,inspired by the greenhouse effect,we report an RT molten salt Li-CO_(2)battery where solar energy can be efficiently harvested and converted into heat that is further localized on the cathode consisting of plasmonic ruthenium(Ru)catalysts and Li_(2)CO_(3)-based products via a greenhouse-like phenomenon.As a result,the solar-driven molten salt Li-CO_(2)battery demonstrates a larger full discharge/charge capacity of 9.5 mA h/8.1 mA h,and a longer cycle lifespan of 250 cycles at 500 mA/g with a limited capacity of 500 mA h/g at RT than the molten salt Li-CO_(2)battery at 130℃.Notably,the average temperature of the cathode increases by 8℃ after discharge to 0.75 mA h,which indicates the infrared radiation from Ru catalysts can be effectively suppressed by discharged Li_(2)CO_(3)-based products.This battery technology paves the way for developing low-temperature molten salt energy storage devices.
基金Project supported by the National Natural Science Foundation of China(22106074)Tianjin Science and Technology Program(23YDTPJC00540,22YJDSS00060)。
文摘Ce-β-Bi_(2)O_(3)/AgI was prepared using solvothermal calcination and in-situ deposition methods.The introduction of Ce can inhibit the conversion of Bi_(2)O_(3)fromβtoαphase at high temperatures,promoting the formation of oxygen vacancies(OVs)in the photocatalyst.OVs can adsorb more dissolved oxygen to promote the formation rate of·O^(-)_(2).Moreover,the interaction between Ce-Bi_(2)O_(3)and AgI results in the formation of Z-scheme heterojunctions,which can broaden the light absorption region,facilitate photogenerated carrier separation and transfer and enhance the ability to produce more active oxygen species(ROS).The morphology,crystal,element distribution and photo-electric chemical properties of the Ce-Bi_(2)O_(3)/AgI were analyzed,and the result shows that the optimal ratio of Ce-Bi_(2)O_(3)/AgI photocatalyst achieves a removal rate of 88.63%(180 min)of tetracycline(TC)(20 mg/L)and 100%(120 min)of methyl orange(MO)(20 mg/L).This work clarified the photocatalytic degradation mechanism,providing a promising avenue for developing photocatalytic composites by rare earth metal doping in environme ntal remediation applications.
基金supported by the Shandong Provincial Natural Science Foundation(ZR2024MD116)National Natural Science Foundation of China(Grant Nos.42174143,42004098)Technology Innovation Leading Program of Shaanxi(No.2024 ZC-YYDP-27).
文摘Subsurface rocks,as complex porous media,exhibit multiscale pore structures and intricate physical properties.Digital rock physics technology has become increasingly influential in the study of subsurface rock properties.Given the multiscale characteristics of rock pore structures,direct three-dimensional imaging at sub-micrometer and nanometer scales is typically infeasible.This study introduces a method for reconstructing porous media using multidimensional data,which combines one-dimensional pore structure parameters with two-dimensional images to reconstruct three-dimensional models.The pore network model(PNM)is stochastically reconstructed using one-dimensional parameters,and a generative adversarial network(GAN)is utilized to equip the PNM with pore morphologies derived from two-dimensional images.The digital rocks generated by this method possess excellent controllability.Using Berea sandstone and Grosmont carbonate samples,we performed digital rock reconstructions based on PNM extracted by the maximum ball algorithm and compared them with stochastically reconstructed PNM.Pore structure parameters,permeability,and formation factors were calculated.The results show that the generated samples exhibit good consistency with real samples in terms of pore morphology,pore structure,and physical properties.Furthermore,our method effectively supplements the micropores not captured in CT images,demonstrating its potential in multiscale carbonate samples.Thus,the proposed reconstruction method is promising for advancing porous media property research.
