Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electro...Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.展开更多
Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active...Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.展开更多
Single atom catalysts supported by two-dimensional(2D)materials,including graphene,g-C_(3)N_(4),and graphdiyne,ex-hibit promising electrocatalytic nitrogen reduction reaction(NRR)activity.Nevertheless,sometimes theore...Single atom catalysts supported by two-dimensional(2D)materials,including graphene,g-C_(3)N_(4),and graphdiyne,ex-hibit promising electrocatalytic nitrogen reduction reaction(NRR)activity.Nevertheless,sometimes theoretical works failed to predict the high activity of NRR of single atom cat-alysts,especially for Fe,Co,Mn,Cu,Ru.In this work,based on DFT calculations,it is suggested that dual-atom sites on N doped graphene(M_(2)@N-graphene)rather than single-atom sites are more likely to be the active sites for NRR.Notably,Fe_(2)@N_(3),Co_(2)@N_(2),Mn_(2)@N_(2),Cu_(2)@N_(1),and Ru_(2)@N_(3)endow the best catalytic activity with corresponding limiting potentials of-0.26,-0.18,-0.17,-0.39,and-0.30 V,re-spectively.Furthermore,on g-C_(3)N_(4)and graphdiyne,triple-atom sites(TAS,M_(3))such as Ru_(3)(Co_(3))@g-C_(3)N_(4)and Ru_(3)(Rh_(3))@graphdiyne are expected to exhibit higher stability and NRR catalytic performance than single-atom sites(SAS)and dual-atom sites(DAS),with corresponding limiting potentials of-0.28,-0.48,-0.24,and-0.23 V.The calculated results with the corresponding experimental potentials indicate that the origin of superior NRR ac-tivity observed in experiments may be contributed by M_(2)or M_(3)on 2D materials.This study provides an in-depth investigation into real active NRR sites of metal atoms supported on 2D materials and contributes to the design of effective NRR catalysts.展开更多
Gallium nitride(GaN)single crystal with prominent electron mobility and heat resistance have great potential in the high temperature integrate electric power systems.However,the sluggish charge storage kinetics and in...Gallium nitride(GaN)single crystal with prominent electron mobility and heat resistance have great potential in the high temperature integrate electric power systems.However,the sluggish charge storage kinetics and inadequate energy densities are bottlenecks to its practical application.Herein,the self-supported GaN/Mn_(3)O_(4) integrated electrode is developed for both energy harvesting and storage under the high temperature environment.The experimental and theoretical calculations results reveal that such integrated structures with Mn-N heterointerface bring abundant active sites and reconstruct low-energy barrier channels for efficient charge transferring,reasonably optimizing the ions adsorption ability and strengthening the structural stability.Consequently,the assembled GaN based supercapacitors deliver the power density of 34.0 mW cm^(-2) with capacitance retention of 81.3%after 10000 cycles at 130℃.This work innovatively correlates the centimeter scale GaN single crystal with ideal theoretical capacity Mn_(3)O_(4) and provides an effective avenue for the follow-up energy storage applications of the wide bandgap semiconductor.展开更多
Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the ma...Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the main catalyst,while Ti_(3)C_(2) MXene served as the co-catalyst.Experimental and theoretical results revealed that Ti_(3)C_(2) MXene introduced electron-rich unsaturated Ti sites,serving as highly active sites for both the adsorption and activation of N_(2) on the Ti_(3)C_(2)/TiO_(2) heterojunction.Furthermore,the 2D/2D Ti_(3)C_(2)/TiO_(2) heterostructure greatly promoted the directional separation and transfer of charge carriers,facilitated by the internal electric field.This structural feature enabled the spatial separation of the N_(2) reduction and H2 O oxidation half-reactions on the distinct surfaces of Ti_(3)C_(2)(001)and TiO_(2)(001),con-sequently reducing the reaction energy barrier for each respective process.The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photo-catalytic NRR activity.As a result,the optimized Ti_(3)C_(2)/TiO_(2) heterojunction exhibited a high NH_(3) produc-tion rate of 24.4μmol g−1 h−1 in the absence of sacrificial agents,representing a remarkable 12.8-fold increase compared to individual TiO_(2) Ns.This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism under-lying surface active sites in the photocatalytic NRR process.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
The kidney is essential for maintaining fluid,electrolyte,and metabolite homeostasis,and for regulating blood pressure.The pig serves as a valuable biomedical model for human renal physiology,offering insights across ...The kidney is essential for maintaining fluid,electrolyte,and metabolite homeostasis,and for regulating blood pressure.The pig serves as a valuable biomedical model for human renal physiology,offering insights across different physiological states.In this study,single-cell RNA sequencing was used to profile 138469 cells from 12 pig kidney samples collected during the embryonic(E),fattening(F),and pregnancy(P)periods,identifying 29 cell types.Proximal tubule(PT)cells exhibited elevated expression of metabolism-related transcription factors(TFs),including GPD1,ACAA1,and AGMAT,with validation across multiple individuals,periods,and species.Fluorescence homologous double-labeling of paraffin sections further confirmed the expression of ACAA1 and AGMAT in PT cells.Comparative analysis of pig and human kidneys revealed a high degree of similarity among corresponding cell types.Analysis of cell-type heterogeneity highlighted the diversity of thick ascending limb(TAL)cells,identifying a TAL subpopulation related to immune function.Additionally,the functional heterogeneity of kidney-resident macrophages(KRM)was explored across different anatomical sites.In the renal medulla,KRM were implicated in phagocytosis and leukocyte activation,whereas in the renal pelvis,they functioned as ligands,recruiting neutrophils with bactericidal activity to the renal pelvis to combat urinary tract infections.展开更多
Two protected sites located on the outskirts of the Sena Oura National Park (PNSO) in West Mayo-Kebbi cover an area of 1800 m2 is pattern choose in pastoral enclave in both village. This study was undertaken to highli...Two protected sites located on the outskirts of the Sena Oura National Park (PNSO) in West Mayo-Kebbi cover an area of 1800 m2 is pattern choose in pastoral enclave in both village. This study was undertaken to highlight the floristic diversity of the herbaceous and woody vegetation on these sites in the offing to know the ability of charge into UBT that most support the park peripheral. It took place on two experimental sites on a natural course in two villages: Wazetelan and Massang. The approach used for the study was a survey using the systematic sampling method and a 30 m × 30 m plot. The survey consisted in listing all the taxa in a floristically homogeneous plot, each assigned the Braun-Blanquet dominance abundance coefficient. These surveys revealed a floristic richness of 73 species, 58 genera, including 46 herbaceous and 26 woody species. The Shannon result gives H1' = 0.12 bit for herbaceous species and H2' = 0.44 bit for woody species, meaning that the herbaceous and woody populations of all the surveys have a very low species diversity, as H' < 3 according to the Shannon index assessment threshold. Herbaceous species are divided into 13 families and 33 genera. The most represented families are Fabaceae (27.3%) and Poaceae (21.9%). Most of the other families (1.3%) have only one species, if any. Herbaceous species are divided into 33 genera grouped into 13 families. The most represented families are Fabaces (16 species), 34%, and Poaceae (12 species), 26%. The 26 woody species, most of which come from itinerant surveys, are distributed across 24 genera and 12 families, the most important of which is Fabaceae with 09 species (34.6%). This floristic assessment, in terms of quantity and quality, has enabled us to estimate the carrying capacity of the two pastoral enclaves in Dari and Goumadji cantons, and to guide the government’s actions with regard to rangeland management.展开更多
As an important pillar of China's industrialization process,the coal industry has not only made contributions to economic growth,but also left a large number of coal mine sites bearing historical memories.These si...As an important pillar of China's industrialization process,the coal industry has not only made contributions to economic growth,but also left a large number of coal mine sites bearing historical memories.These sites are not only the witness of the industrial civilization,but also the potential resources for urban renewal and industrial transformation.展开更多
Disrupting the symmetric electron distribution of porphyrin-like Fe singleatom catalysts has been considered as an effective way to harvest high intrinsic activity.Understanding the catalytic performance governed by g...Disrupting the symmetric electron distribution of porphyrin-like Fe singleatom catalysts has been considered as an effective way to harvest high intrinsic activity.Understanding the catalytic performance governed by geometric microstrains is highly desirable for further optimization of such efficient sites.Here,we decipher the crucial role of local microstrain in boosting intrinsic activity and durability of asymmetric Fe single-atom catalysts(Fe-N_(3)S_(1))by replacing one N atom with S atom.The high-curvature hollow carbon nanosphere substrate introduces 1.3%local compressive strain to Fe-N bonds and 1.5%tensile strain to Fe-S bonds,downshifting the d-band center and accelerating the kinetics of*OH reduction.Consequently,highly curved Fe-N_(3)S_(1)sites anchored on hollow carbon nanosphere(FeNS-HNS-20)exhibit negligible current loss,a high half-wave potential of 0.922 V vs.RHE and turnover frequency of 6.2 e^(−1)s^(−1)site−1,which are 53 mV more positive and 1.7 times that of flat Fe-N-S counterpart,respectively.More importantly,multiple operando spectroscopies monitored the dynamic optimization of strained Fe-N_(3)S_(1)sites into Fe-N_(3)sites,further mitigating the overadsorption of*OH intermediates.This work not only sheds new light on local microstrain-induced catalytic enhancement,but also provides a plausible direction for optimizing efficient asymmetric sites via geometric configurations.展开更多
Enhancing the catalytic hydrolysis efficiency of microcystins(MCs)at ambient temperature has been a persistent challenge in water treatment.We employed N_(2)/low-temperature plasma technology to modify the surface of ...Enhancing the catalytic hydrolysis efficiency of microcystins(MCs)at ambient temperature has been a persistent challenge in water treatment.We employed N_(2)/low-temperature plasma technology to modify the surface of natural pyrites(NP),and the resulting nitrogenmodified pyrites(NPN)with a nanorod structure and new Fe-Nx sites are more efficient for the hydrolysis of microcystins-LR(MC-LR).Kinetic experiments revealed that NPN exhibited significantly higher hydrolysis activity(k_(obs)=0.1471 h^(-1))than NP(0.0914 h^(-1)).Liquid chromatography-mass spectrometry(LC/MS)for the intermediates produced by hydrolyzing MC-LR,in situ attenuated total reflectance Fourier transform infrared spectroscopy(in situ ATR-FTIR)and X-ray photoelectron spectroscopy(XPS)analysis unfolded that the Fe and N atoms of Fe-Nx sites on the surface act of NPN as Lewis acid and Bronsted basic respectively,selectively breaking amide bond on MC-LR molecule.This study demonstrates the effectiveness of plasma technology in modifying mineral materials to enhance their catalytic activity,providing a new method for eliminating MCs in practical water treatment.展开更多
Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimeriz...Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites.Herein,we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd_(1)-O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H∗utilization site,which synchronously inhibits the H-H dimerization and the competitive adsorption of water molecule and targeted reactants.Experiments and theoretical calculations revealed that the Ti-O sites could synergistically dissociate water to H∗,which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate.These Pd_(1)-O-Ti dual sites delivered almost 100%bromate reduction efficiency with a rate constant of 1.57 h^(-1),far superior to those of Pdn-O-Ti with adjacent Pd sites(0.52 h^(-1)),Pd_(1)-N-C with single sites(0.04 h^(-1))and commercial Pd/C(0.18 h^(-1)),respectively.This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions,and provide new insights in improving H∗ utilization for environmental remediation.展开更多
Ground response analysis and determination of site-specific ground motion parameters are necessary for evaluating seismic loads to enable sustainable design of aboveground and underground structures,particularly in de...Ground response analysis and determination of site-specific ground motion parameters are necessary for evaluating seismic loads to enable sustainable design of aboveground and underground structures,particularly in deep overburden sites.This study investigates the influence of bedrock interface conditions and depth of soil deposits on obtained site-specific ground motion parameters.Employing the one-dimensional seismic response analysis program SOILQUAKE,the ground responses of five representative soil profiles and 1050 case studies are calculated considering three different site models of seismic input interfaces.The analysis employs the actual bedrock interface with a shear wave velocity of 760 m/s as the reference input bedrock interface.The results illustrate that the selection of the bedrock interface condition significantly affects the seismic response on the ground surface of deep overburden sites.Specifically,the ground surface acceleration response spectra at longer periods are notably smaller compared to those at the actual bedrock site.This may present a challenge for designing long-period high-rise buildings situated in deep overburden sites.It is recommended to select a seismic input bedrock interface closely approximating the actual bedrock depth when conducting seismic response analyses for deep overburden sites.展开更多
Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conve...Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conversion is imperative yet quite challenging.This critical review summarizes recent advances in porous photo-responsive polymers,including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs),and conjugated microporous polymers(CMPs),those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO_(2)reduction.Additionally,special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance.The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity,as well as for the design of better photocatalysts for CO_(2)reduction.展开更多
Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value ...Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution.Herein,we present a viable strategy to recycle Pb and iron(Fe)from Pb-Zn slags for the fabrication of efficient methylammonium lead tri-iodide(r-MAPbI_(3))piezocatalysts with single-atom Fe-N_(4) sites.Intriguingly,atomically dispersed Fe sites from Pb-Zn slags,which coordinated with N in the neighboring four CH3NH3 to form the FeN_(4) configuration,were detected in the as-obtained r-MAPbI_(3) by synchrotron X-ray absorption spectroscopy.The introduction of Fe single atoms amplified the polarization of MAPbI_(3) and upshifted the d-band center of MAPbI_(3).This not only enhanced the piezoelectric response of MAPbI_(3) but also promoted the proton transfer during the hydrogen evolution process.Due to the decoration of Fe single atoms,r-MAPbI_(3) showed a pronounced H2 yield of 322.4μmol g^(−1) h^(−1),which was 2.52 times that of MAPbI_(3) synthesized using commercially available reagents.This simple yet robust strategy to manufactureMAPbI_(3) piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.展开更多
The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(N...The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(NH_(3)).However,this process faces significant challenges in achieving industrial application due to mismatched reaction kinetics involved in the conversion of NO_(3)^(-)to NO_(2)^(-),the formation of active hydrogen(H^(*))via water dissociation,and the stepwise hydrogenation processes.In this study,we developed a trimetallic CuCoRu catalyst with multiple active sites to enhance the selective NH_(3)synthesis at industrial-scale current density,where Cu primarily catalyzes the reduction of NO_(3)^(-)to NO_(2)^(-),Co facilitates the deep hydrogenation of NO_(2)^(-)to NH_(3),and Ru promotes water dissociation to generate H^(*),effectively bridging the aforementioned processes.The optimized CuCoRu catalyst achieves near-100%NH_(3)Faradaic efficiency with an NH_(3)yield rate of 14.6 mmol h^(-1)cm^(-2)at a current density of 2.5 A cm^(-2).The practical application in simulated wastewater with different NO_(3)^(-)concentrations and in the membrane electrode assembly demonstrates great potential for industrial application.展开更多
The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is...The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is a promising candidate [1,2]. Some noblemetal-based (e.g., Pt, Pd and Rh) catalysts exhibit significant catalytic activity to the conversion reaction of these biomass.展开更多
The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system...The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system.Phosphorus(P)and hydrocarbons(HCs)present in the exhaust have negative impacts on the catalysts.To enhance the resistance of Cu-SSZ-39 catalysts to P and HCs,various rare earth metals were doped.Loading of 1 wt%Ce on the Cu-SSZ-39 catalyst improves the resistance to P and HCs simultaneously.The promotion mechanism was investigated through H_(2)-temperature programmed reduction(H_(2)-TPR),ultraviolet visible diffuse reflectance spectroscopy(UV-vis-DRS),diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),X-ray photoelectron spectroscopy(XPS),energy dispersive spectroscopy(EDS)and theoretical calculation.On the one hand,Ce species can act as sacrificial sites,preferentially binding with P.On the other hand,Ce doping induces the formation of CuO species,promoting the oxidation of C_(3)H_(6)and preventing the consumption of NH_(3)from the reaction with C_(3)H_(6).Ce acting as bi-functional sites enhances the P and HCs resistance of Cu-SSZ-39 catalysts,further brightening its practical application.展开更多
Engineering the local electronic structure of atomic-dispersed catalytic sites plays a critical role in selective photocatalysis.Here,we show the regulation of local electronic structure of atomic-dispersed Ni sites b...Engineering the local electronic structure of atomic-dispersed catalytic sites plays a critical role in selective photocatalysis.Here,we show the regulation of local electronic structure of atomic-dispersed Ni sites by forming oxygen-bridged diatomic Ni-O-Ni confined in MOF-derived TiO_(2)(O-Ni_(2)/TiO_(2))via oxalic acid chelation.Among them,MOF-derived TiO_(2)scaffold provides a highly porous structure,supporting highly exposed active sites of Ni-O-Ni dimers linked by oxygen bridges.Density functional theory calculations show that the Ni-O-Ni sites regulate the local electronic structure of Ni sites,promoting the adsorption and activation of reactant molecules.Ultrafast spectroscopy shows that,in comparison with monomeric Ni/TiO_(2),the strong interaction in dimeric O-Ni_(2)/TiO_(2)tends to bring forth a more pronounced suppression of photogenerated electron-hole recombination,beneficial for achieving better charge separation and transfer as desired.As a direct outcome,the O-Ni_(2)/TiO_(2)photocatalyst has shown enhanced photocatalytic activity and selectivity in glycerol reforming reaction,with the average rates of H_(2)and CO evolution attaining as high as 2542.6 and 361.7μmol g^(-1)h^(-1),respectively,along with a remarkable selectivity of96.1%towards the syngas production(under a 365-nm light irradiation).Notably,the H_(2)and CO yields of the O-Ni_(2)/TiO_(2)photocatalyst are 3.9 and 6.7 times higher than those of the Ni/TiO_(2)photocatalyst,respectively.This study highlights the beneficial role of engineering the local electronic structure of atomicdispersed catalytic sites and provides an effective way for selective photocatalytic biomass conversion.展开更多
Conventional gas sensing materials(e.g.,metal oxides)suffer from deficient sensitivity and serve cross-sensitivity issues due to the lack of efficient adsorption sites.Herein,the heteroatom atomically doping strategy ...Conventional gas sensing materials(e.g.,metal oxides)suffer from deficient sensitivity and serve cross-sensitivity issues due to the lack of efficient adsorption sites.Herein,the heteroatom atomically doping strategy is demonstrated to significantly enhance the sensing performance of metal oxides-based gas sensing materials.Specifically,the Sn atoms were incorporated into porous Fe_(2)O_(3)in the form of atomically dispersed sites.As revealed by X-ray absorption spectroscopy and atomic-resolution scanning transmission electron microscopy,these Sn atoms successfully occupy the Fe sites in the Fe_(2)O_(3)lattice,forming the unique Sn-O-Fe sites.Compared to Fe-O-Fe sites(from bare Fe_(2)O_(3))and Sn-O-Sn sites(from SnO_(2)/Fe_(2)O_(3)with high Sn loading),the Sn-O-Fe sites on porous Fe_(2)O_(3)exhibit a superior sensitivity(Rg/Ra=2646.6)to 1 ppm NO_(2),along with dramatically increased selectivity and ultra-low limits of detection(10 ppb).Further theoretical calculations suggest that the strong adsorption of NO_(2)on Sn-O-Fe sites(N atom on Sn site,O atom on Fe site)contributes a more efficient gas response,compared to NO_(2)on Fe-O-Fe sites and other gases on Sn-O-Fe sites.Moreover,the incorporated Sn atoms reduce the bandgap of Fe_(2)O_(3),not only facilitating the electron release but also increasing the NO_(2)adsorption at a low working temperature(150°C).This work introduces an effective strategy to construct effective adsorption sites that show a unique response to specific gas molecules,potentially promoting the rational design of atomically modified gas sensing materials with high sensitivity and high selectivity.展开更多
基金the financial support from the National Natural Science Foundation of China(52172110,52472231,52311530113)Shanghai"Science and Technology Innovation Action Plan"intergovernmental international science and technology cooperation project(23520710600)+1 种基金Science and Technology Commission of Shanghai Municipality(22DZ1205600)the Central Guidance on Science and Technology Development Fund of Zhejiang Province(2024ZY01011)。
文摘Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols.Herein,we report efficient electrocatalytic oxidations of saturated alcohols(C_(1)-C_(6))to selectively form formate using Ni Co hydroxide(Ni Co-OH)derived Ni Co_(2)O_(4)solid-acid electrocatalysts with balanced Lewis acid(LASs)and Brønsted acid sites(BASs).Thermal treatment transforms BASs-rich(89.6%)Ni Co-OH into Ni Co_(2)O_(4)with nearly equal distribution of LASs(53.1%)and BASs(46.9%)which synergistically promote adsorption and activation of OH-and alcohol molecules for enhanced oxidation activity.In contrast,BASs-enriched Ni Co-OH facilitates formation of higher valence metal sites,beneficial for water oxidation.The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6alcohols increases as increased number of hydroxyl groups and decreased HOMO-LUMO gaps:methanol(C_(1))<ethylene glycol(C_(2))<glycerol(C3)<meso-erythritol(C4)<xylitol(C5)<sorbitol(C6),while the formate selectivity shows the opposite trend from 100 to 80%.This study unveils synergistic roles of LASs and BASs,as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.
文摘Molecular recognition of bioreceptors and enzymes relies on orthogonal interactions with small molecules within their cavity. To date, Chinese scientists have developed three types of strategies for introducing active sites inside the cavity of macrocyclic arenes to better mimic molecular recognition of bioreceptors and enzymes.The editorial aims to enlighten scientists in this field when they develop novel macrocycles for molecular recognition, supramolecular assembly, and applications.
基金partially supported by the National Natural Science Foundation of China(Nos.22373092,22288201)CAS Project for Young Scientists in Basic Research(YSBR-051)+1 种基金Innovation Program for Quantum Science and Technology(2021ZD0303306)supported by University of Science and Technology of China Tang Scholarship and State Scholarship Fund(202206345005)。
文摘Single atom catalysts supported by two-dimensional(2D)materials,including graphene,g-C_(3)N_(4),and graphdiyne,ex-hibit promising electrocatalytic nitrogen reduction reaction(NRR)activity.Nevertheless,sometimes theoretical works failed to predict the high activity of NRR of single atom cat-alysts,especially for Fe,Co,Mn,Cu,Ru.In this work,based on DFT calculations,it is suggested that dual-atom sites on N doped graphene(M_(2)@N-graphene)rather than single-atom sites are more likely to be the active sites for NRR.Notably,Fe_(2)@N_(3),Co_(2)@N_(2),Mn_(2)@N_(2),Cu_(2)@N_(1),and Ru_(2)@N_(3)endow the best catalytic activity with corresponding limiting potentials of-0.26,-0.18,-0.17,-0.39,and-0.30 V,re-spectively.Furthermore,on g-C_(3)N_(4)and graphdiyne,triple-atom sites(TAS,M_(3))such as Ru_(3)(Co_(3))@g-C_(3)N_(4)and Ru_(3)(Rh_(3))@graphdiyne are expected to exhibit higher stability and NRR catalytic performance than single-atom sites(SAS)and dual-atom sites(DAS),with corresponding limiting potentials of-0.28,-0.48,-0.24,and-0.23 V.The calculated results with the corresponding experimental potentials indicate that the origin of superior NRR ac-tivity observed in experiments may be contributed by M_(2)or M_(3)on 2D materials.This study provides an in-depth investigation into real active NRR sites of metal atoms supported on 2D materials and contributes to the design of effective NRR catalysts.
基金supported by NSFC(Grant No.52202265,52302004,52472010,62434010)the Taishan Scholars Program of Shandong Province(tsqn202306330)+1 种基金Shenzhen Science and Technology Program(JCYJ20230807094009018)Xiaomi Young Talents Program(2023XM06).
文摘Gallium nitride(GaN)single crystal with prominent electron mobility and heat resistance have great potential in the high temperature integrate electric power systems.However,the sluggish charge storage kinetics and inadequate energy densities are bottlenecks to its practical application.Herein,the self-supported GaN/Mn_(3)O_(4) integrated electrode is developed for both energy harvesting and storage under the high temperature environment.The experimental and theoretical calculations results reveal that such integrated structures with Mn-N heterointerface bring abundant active sites and reconstruct low-energy barrier channels for efficient charge transferring,reasonably optimizing the ions adsorption ability and strengthening the structural stability.Consequently,the assembled GaN based supercapacitors deliver the power density of 34.0 mW cm^(-2) with capacitance retention of 81.3%after 10000 cycles at 130℃.This work innovatively correlates the centimeter scale GaN single crystal with ideal theoretical capacity Mn_(3)O_(4) and provides an effective avenue for the follow-up energy storage applications of the wide bandgap semiconductor.
基金supported by the National Natural Science Foundation of China(No.21773089)the Henan Center for Outstanding Overseas Scientist(No.GZS2024004).
文摘Herein,a new type of two-dimensional(2D)/2D Ti_(3)C_(2)/TiO_(2) heterojunction was developed for efficient photocatalytic nitrogen reduction reaction(NRR),in which TiO_(2) nanosheets(TiO_(2) Ns)were designed as the main catalyst,while Ti_(3)C_(2) MXene served as the co-catalyst.Experimental and theoretical results revealed that Ti_(3)C_(2) MXene introduced electron-rich unsaturated Ti sites,serving as highly active sites for both the adsorption and activation of N_(2) on the Ti_(3)C_(2)/TiO_(2) heterojunction.Furthermore,the 2D/2D Ti_(3)C_(2)/TiO_(2) heterostructure greatly promoted the directional separation and transfer of charge carriers,facilitated by the internal electric field.This structural feature enabled the spatial separation of the N_(2) reduction and H2 O oxidation half-reactions on the distinct surfaces of Ti_(3)C_(2)(001)and TiO_(2)(001),con-sequently reducing the reaction energy barrier for each respective process.The synergistic effects arising from the interface and surface interactions within the heterojunction conspicuously improved the photo-catalytic NRR activity.As a result,the optimized Ti_(3)C_(2)/TiO_(2) heterojunction exhibited a high NH_(3) produc-tion rate of 24.4μmol g−1 h−1 in the absence of sacrificial agents,representing a remarkable 12.8-fold increase compared to individual TiO_(2) Ns.This work provides new insights into rational design of high-performance heterogeneous photocatalysts and offers a deeper understanding of the mechanism under-lying surface active sites in the photocatalytic NRR process.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
基金supported by the International Cooperation and Exchange Program of the National Natural Science Foundation of China(32261133531)。
文摘The kidney is essential for maintaining fluid,electrolyte,and metabolite homeostasis,and for regulating blood pressure.The pig serves as a valuable biomedical model for human renal physiology,offering insights across different physiological states.In this study,single-cell RNA sequencing was used to profile 138469 cells from 12 pig kidney samples collected during the embryonic(E),fattening(F),and pregnancy(P)periods,identifying 29 cell types.Proximal tubule(PT)cells exhibited elevated expression of metabolism-related transcription factors(TFs),including GPD1,ACAA1,and AGMAT,with validation across multiple individuals,periods,and species.Fluorescence homologous double-labeling of paraffin sections further confirmed the expression of ACAA1 and AGMAT in PT cells.Comparative analysis of pig and human kidneys revealed a high degree of similarity among corresponding cell types.Analysis of cell-type heterogeneity highlighted the diversity of thick ascending limb(TAL)cells,identifying a TAL subpopulation related to immune function.Additionally,the functional heterogeneity of kidney-resident macrophages(KRM)was explored across different anatomical sites.In the renal medulla,KRM were implicated in phagocytosis and leukocyte activation,whereas in the renal pelvis,they functioned as ligands,recruiting neutrophils with bactericidal activity to the renal pelvis to combat urinary tract infections.
文摘Two protected sites located on the outskirts of the Sena Oura National Park (PNSO) in West Mayo-Kebbi cover an area of 1800 m2 is pattern choose in pastoral enclave in both village. This study was undertaken to highlight the floristic diversity of the herbaceous and woody vegetation on these sites in the offing to know the ability of charge into UBT that most support the park peripheral. It took place on two experimental sites on a natural course in two villages: Wazetelan and Massang. The approach used for the study was a survey using the systematic sampling method and a 30 m × 30 m plot. The survey consisted in listing all the taxa in a floristically homogeneous plot, each assigned the Braun-Blanquet dominance abundance coefficient. These surveys revealed a floristic richness of 73 species, 58 genera, including 46 herbaceous and 26 woody species. The Shannon result gives H1' = 0.12 bit for herbaceous species and H2' = 0.44 bit for woody species, meaning that the herbaceous and woody populations of all the surveys have a very low species diversity, as H' < 3 according to the Shannon index assessment threshold. Herbaceous species are divided into 13 families and 33 genera. The most represented families are Fabaceae (27.3%) and Poaceae (21.9%). Most of the other families (1.3%) have only one species, if any. Herbaceous species are divided into 33 genera grouped into 13 families. The most represented families are Fabaces (16 species), 34%, and Poaceae (12 species), 26%. The 26 woody species, most of which come from itinerant surveys, are distributed across 24 genera and 12 families, the most important of which is Fabaceae with 09 species (34.6%). This floristic assessment, in terms of quantity and quality, has enabled us to estimate the carrying capacity of the two pastoral enclaves in Dari and Goumadji cantons, and to guide the government’s actions with regard to rangeland management.
文摘As an important pillar of China's industrialization process,the coal industry has not only made contributions to economic growth,but also left a large number of coal mine sites bearing historical memories.These sites are not only the witness of the industrial civilization,but also the potential resources for urban renewal and industrial transformation.
基金supported by the Natural Science Foundation of Shandong Province (ZR2024JQ004)the National Natural Science Foundation of China (22108306, 22478432)Taishan Scholars Program of Shandong Province
文摘Disrupting the symmetric electron distribution of porphyrin-like Fe singleatom catalysts has been considered as an effective way to harvest high intrinsic activity.Understanding the catalytic performance governed by geometric microstrains is highly desirable for further optimization of such efficient sites.Here,we decipher the crucial role of local microstrain in boosting intrinsic activity and durability of asymmetric Fe single-atom catalysts(Fe-N_(3)S_(1))by replacing one N atom with S atom.The high-curvature hollow carbon nanosphere substrate introduces 1.3%local compressive strain to Fe-N bonds and 1.5%tensile strain to Fe-S bonds,downshifting the d-band center and accelerating the kinetics of*OH reduction.Consequently,highly curved Fe-N_(3)S_(1)sites anchored on hollow carbon nanosphere(FeNS-HNS-20)exhibit negligible current loss,a high half-wave potential of 0.922 V vs.RHE and turnover frequency of 6.2 e^(−1)s^(−1)site−1,which are 53 mV more positive and 1.7 times that of flat Fe-N-S counterpart,respectively.More importantly,multiple operando spectroscopies monitored the dynamic optimization of strained Fe-N_(3)S_(1)sites into Fe-N_(3)sites,further mitigating the overadsorption of*OH intermediates.This work not only sheds new light on local microstrain-induced catalytic enhancement,but also provides a plausible direction for optimizing efficient asymmetric sites via geometric configurations.
基金supported by the National Natural Science Foundation of China(Nos.22076098,22376118 and 21577078)the Outstanding Youth Project of the Natural Science Foundation of Hubei Province(2023AFA054)the 111 Project of China(No.D20015).
文摘Enhancing the catalytic hydrolysis efficiency of microcystins(MCs)at ambient temperature has been a persistent challenge in water treatment.We employed N_(2)/low-temperature plasma technology to modify the surface of natural pyrites(NP),and the resulting nitrogenmodified pyrites(NPN)with a nanorod structure and new Fe-Nx sites are more efficient for the hydrolysis of microcystins-LR(MC-LR).Kinetic experiments revealed that NPN exhibited significantly higher hydrolysis activity(k_(obs)=0.1471 h^(-1))than NP(0.0914 h^(-1)).Liquid chromatography-mass spectrometry(LC/MS)for the intermediates produced by hydrolyzing MC-LR,in situ attenuated total reflectance Fourier transform infrared spectroscopy(in situ ATR-FTIR)and X-ray photoelectron spectroscopy(XPS)analysis unfolded that the Fe and N atoms of Fe-Nx sites on the surface act of NPN as Lewis acid and Bronsted basic respectively,selectively breaking amide bond on MC-LR molecule.This study demonstrates the effectiveness of plasma technology in modifying mineral materials to enhance their catalytic activity,providing a new method for eliminating MCs in practical water treatment.
基金supported by the National Natural Science Foundation of China(Nos.U22A20402,U21A20286,and 22102100)the Key Program of Shenzhen Science and Technology Commission(No.JCYJ20220818095601002)the Natural Science Foundation of Shanghai(No.22ZR1431700).
文摘Atomic hydrogen(H∗)plays a crucial role in electrochemical reduction technology towards various environmental and energy applications,but suffers from low utilization efficiency arisen from the undesirable H-H dimerization and the competitive adsorption between water molecule with reactants on the traditional adjacent catalytic sites.Herein,we anchored Pd single atoms on the naturally formed titanium oxide of titanium foam to construct Pd_(1)-O-Ti dual-site electrocatalyst with spatially isolated water dissociation and H∗utilization site,which synchronously inhibits the H-H dimerization and the competitive adsorption of water molecule and targeted reactants.Experiments and theoretical calculations revealed that the Ti-O sites could synergistically dissociate water to H∗,which overflowed to nearby Pd single-atom sites for designed reduction reactions and utilization benefiting from the hydrogen spillover ability of titanium oxide substrate.These Pd_(1)-O-Ti dual sites delivered almost 100%bromate reduction efficiency with a rate constant of 1.57 h^(-1),far superior to those of Pdn-O-Ti with adjacent Pd sites(0.52 h^(-1)),Pd_(1)-N-C with single sites(0.04 h^(-1))and commercial Pd/C(0.18 h^(-1)),respectively.This study sheds light on the importance of integrating synergistic active sites for complicated electrochemical reactions,and provide new insights in improving H∗ utilization for environmental remediation.
基金supported by the National Natural Science Foundation of China(Nos.52408435,52278384)。
文摘Ground response analysis and determination of site-specific ground motion parameters are necessary for evaluating seismic loads to enable sustainable design of aboveground and underground structures,particularly in deep overburden sites.This study investigates the influence of bedrock interface conditions and depth of soil deposits on obtained site-specific ground motion parameters.Employing the one-dimensional seismic response analysis program SOILQUAKE,the ground responses of five representative soil profiles and 1050 case studies are calculated considering three different site models of seismic input interfaces.The analysis employs the actual bedrock interface with a shear wave velocity of 760 m/s as the reference input bedrock interface.The results illustrate that the selection of the bedrock interface condition significantly affects the seismic response on the ground surface of deep overburden sites.Specifically,the ground surface acceleration response spectra at longer periods are notably smaller compared to those at the actual bedrock site.This may present a challenge for designing long-period high-rise buildings situated in deep overburden sites.It is recommended to select a seismic input bedrock interface closely approximating the actual bedrock depth when conducting seismic response analyses for deep overburden sites.
基金National Natural Science Foundation of China(No.22005154)for financial support。
文摘Photocatalytic CO_(2)reduction reaction(CO_(2)RR)is one of the promising strategies for sustainably producing solar fuels.The precise identification of catalytic sites and the enhancement of photocatalytic CO_(2)conversion is imperative yet quite challenging.This critical review summarizes recent advances in porous photo-responsive polymers,including covalent organic frameworks(COFs),covalent triazine frameworks(CTFs),and conjugated microporous polymers(CMPs),those can be rationally designed from the molecular level for visible-light-driven photocatalytic CO_(2)reduction.Additionally,special emphasis is placed on how the well-defined active sites on these polymers can influence their properties and photocatalytic performance.The precise regulation and control of microenvironments and electronic properties of metal active centers are crucial for boosting catalytic efficiency and selectivity,as well as for the design of better photocatalysts for CO_(2)reduction.
基金supported by the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(No.52121004,U23B20166)Guangdong Basic and Applied Basic Research Foundation(2024A1515030039,2025A1515010312).
文摘Lead(Pb)-zinc(Zn)slags contain large amounts of Pb,causing irreversible damage to the environment.Therefore,developing an effective strategy to extract Pb from Pb-Zn slags and convert them into a renewable high-value catalyst not only solves the energy crisis but also reduces environmental pollution.Herein,we present a viable strategy to recycle Pb and iron(Fe)from Pb-Zn slags for the fabrication of efficient methylammonium lead tri-iodide(r-MAPbI_(3))piezocatalysts with single-atom Fe-N_(4) sites.Intriguingly,atomically dispersed Fe sites from Pb-Zn slags,which coordinated with N in the neighboring four CH3NH3 to form the FeN_(4) configuration,were detected in the as-obtained r-MAPbI_(3) by synchrotron X-ray absorption spectroscopy.The introduction of Fe single atoms amplified the polarization of MAPbI_(3) and upshifted the d-band center of MAPbI_(3).This not only enhanced the piezoelectric response of MAPbI_(3) but also promoted the proton transfer during the hydrogen evolution process.Due to the decoration of Fe single atoms,r-MAPbI_(3) showed a pronounced H2 yield of 322.4μmol g^(−1) h^(−1),which was 2.52 times that of MAPbI_(3) synthesized using commercially available reagents.This simple yet robust strategy to manufactureMAPbI_(3) piezocatalysts paves a novel way to the large-scale and value-added consumption of Pb-containing waste residues.
基金support from the National Key R&D Program of China(2020YFA0710000)the National Natural Science Foundation of China(22278307,22008170,22222808,21978200)the Haihe Laboratory of Sustainable Chemical Transformations。
文摘The electrochemical nitrate reduction reaction(NO_(3)^(-)RR)represents a promising and environmentally friendly approach for both the removal of nitrate(NO_(3)^(-))pollutants and the production of high-value ammonia(NH_(3)).However,this process faces significant challenges in achieving industrial application due to mismatched reaction kinetics involved in the conversion of NO_(3)^(-)to NO_(2)^(-),the formation of active hydrogen(H^(*))via water dissociation,and the stepwise hydrogenation processes.In this study,we developed a trimetallic CuCoRu catalyst with multiple active sites to enhance the selective NH_(3)synthesis at industrial-scale current density,where Cu primarily catalyzes the reduction of NO_(3)^(-)to NO_(2)^(-),Co facilitates the deep hydrogenation of NO_(2)^(-)to NH_(3),and Ru promotes water dissociation to generate H^(*),effectively bridging the aforementioned processes.The optimized CuCoRu catalyst achieves near-100%NH_(3)Faradaic efficiency with an NH_(3)yield rate of 14.6 mmol h^(-1)cm^(-2)at a current density of 2.5 A cm^(-2).The practical application in simulated wastewater with different NO_(3)^(-)concentrations and in the membrane electrode assembly demonstrates great potential for industrial application.
文摘The quest for sustainable energy solutions has intensified the search for alternative feedstocks that can supplement or replace fossil fuels. Obtaining fuels or chemicals through the conversion of renewable biomass is a promising candidate [1,2]. Some noblemetal-based (e.g., Pt, Pd and Rh) catalysts exhibit significant catalytic activity to the conversion reaction of these biomass.
基金Project supported by the National Key R&D Program of China(2023YFC3707201)National Natural Science Foundation of China(52200136,52270112,22106172)National Energy-Saving and Low-Carbon Materials Production and Application Demonstration Platform Program(TC220H06N)。
文摘The abatement of NO_(x)from diesel vehicle exhaust is of great importance for improving the atmospheric enviro nment.Cu-SSZ-39 zeolites possess the potential for application in the diesel vehicle aftertreatment system.Phosphorus(P)and hydrocarbons(HCs)present in the exhaust have negative impacts on the catalysts.To enhance the resistance of Cu-SSZ-39 catalysts to P and HCs,various rare earth metals were doped.Loading of 1 wt%Ce on the Cu-SSZ-39 catalyst improves the resistance to P and HCs simultaneously.The promotion mechanism was investigated through H_(2)-temperature programmed reduction(H_(2)-TPR),ultraviolet visible diffuse reflectance spectroscopy(UV-vis-DRS),diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS),X-ray photoelectron spectroscopy(XPS),energy dispersive spectroscopy(EDS)and theoretical calculation.On the one hand,Ce species can act as sacrificial sites,preferentially binding with P.On the other hand,Ce doping induces the formation of CuO species,promoting the oxidation of C_(3)H_(6)and preventing the consumption of NH_(3)from the reaction with C_(3)H_(6).Ce acting as bi-functional sites enhances the P and HCs resistance of Cu-SSZ-39 catalysts,further brightening its practical application.
基金supported by the National Key R&D Program of China(2022YFA1503003)the National Natural Science Foundation of China(U24A20550,52273264,22173090)+2 种基金the Youth Scienceof China(22409056)the Innovation Program for Quantum Science and Technology(2021ZD0303303)the Key Project of the Heilongjiang Provincial Natural Science Foundation(ZD2024B001)。
文摘Engineering the local electronic structure of atomic-dispersed catalytic sites plays a critical role in selective photocatalysis.Here,we show the regulation of local electronic structure of atomic-dispersed Ni sites by forming oxygen-bridged diatomic Ni-O-Ni confined in MOF-derived TiO_(2)(O-Ni_(2)/TiO_(2))via oxalic acid chelation.Among them,MOF-derived TiO_(2)scaffold provides a highly porous structure,supporting highly exposed active sites of Ni-O-Ni dimers linked by oxygen bridges.Density functional theory calculations show that the Ni-O-Ni sites regulate the local electronic structure of Ni sites,promoting the adsorption and activation of reactant molecules.Ultrafast spectroscopy shows that,in comparison with monomeric Ni/TiO_(2),the strong interaction in dimeric O-Ni_(2)/TiO_(2)tends to bring forth a more pronounced suppression of photogenerated electron-hole recombination,beneficial for achieving better charge separation and transfer as desired.As a direct outcome,the O-Ni_(2)/TiO_(2)photocatalyst has shown enhanced photocatalytic activity and selectivity in glycerol reforming reaction,with the average rates of H_(2)and CO evolution attaining as high as 2542.6 and 361.7μmol g^(-1)h^(-1),respectively,along with a remarkable selectivity of96.1%towards the syngas production(under a 365-nm light irradiation).Notably,the H_(2)and CO yields of the O-Ni_(2)/TiO_(2)photocatalyst are 3.9 and 6.7 times higher than those of the Ni/TiO_(2)photocatalyst,respectively.This study highlights the beneficial role of engineering the local electronic structure of atomicdispersed catalytic sites and provides an effective way for selective photocatalytic biomass conversion.
基金supported by the National Key Research and Development Project of China(Grant No.2022YFB3205500)the National Natural Science Foundation of China(Grant No.12275190,12105201)+2 种基金Jiangsu Funding Program for Excellent Postdoctoral Talent(Grant No.2024ZB723)the Shenzhen Research Funding Program(JCYJ20230807154402004)supported by the Collaborative Innovation Center of Suzhou Nano Science&Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD),the 111 Project,the Joint International Research Laboratory of Carbon-Based Functional Materials and Devices,and the Suzhou Key Laboratory of Functional Nano&Soft Materials and Soochow University-Western University Centre for Synchrotron Radiation Research.
文摘Conventional gas sensing materials(e.g.,metal oxides)suffer from deficient sensitivity and serve cross-sensitivity issues due to the lack of efficient adsorption sites.Herein,the heteroatom atomically doping strategy is demonstrated to significantly enhance the sensing performance of metal oxides-based gas sensing materials.Specifically,the Sn atoms were incorporated into porous Fe_(2)O_(3)in the form of atomically dispersed sites.As revealed by X-ray absorption spectroscopy and atomic-resolution scanning transmission electron microscopy,these Sn atoms successfully occupy the Fe sites in the Fe_(2)O_(3)lattice,forming the unique Sn-O-Fe sites.Compared to Fe-O-Fe sites(from bare Fe_(2)O_(3))and Sn-O-Sn sites(from SnO_(2)/Fe_(2)O_(3)with high Sn loading),the Sn-O-Fe sites on porous Fe_(2)O_(3)exhibit a superior sensitivity(Rg/Ra=2646.6)to 1 ppm NO_(2),along with dramatically increased selectivity and ultra-low limits of detection(10 ppb).Further theoretical calculations suggest that the strong adsorption of NO_(2)on Sn-O-Fe sites(N atom on Sn site,O atom on Fe site)contributes a more efficient gas response,compared to NO_(2)on Fe-O-Fe sites and other gases on Sn-O-Fe sites.Moreover,the incorporated Sn atoms reduce the bandgap of Fe_(2)O_(3),not only facilitating the electron release but also increasing the NO_(2)adsorption at a low working temperature(150°C).This work introduces an effective strategy to construct effective adsorption sites that show a unique response to specific gas molecules,potentially promoting the rational design of atomically modified gas sensing materials with high sensitivity and high selectivity.
