Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding...Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding photocatalytic activities has become a research hotspot in this field.In this study,we prepared a series of photocatalysts in which BiOCl nanosheets were modified with carbon quantum dots(CQDs)to form CQDs/BiOCl composites by using a simple solvothermal method.The photocatalytic performance of the resulting CQDs/BiOCl composite photocatalysts was assessed by rhodamine B and tetracycline degradation under visible-light irradiation.Compared with bare BiOCl,the photocatalytic activity of the CQDs/BiOCl composites was significantly enhanced,and the 5 wt%CQDs/BiOCl composite exhibited the highest photocatalytic activity with a degradation efficiency of 94.5%after 30 min of irradiation.Moreover,photocatalytic N_(2)reduction performance was significantly improved after introducing CQDs.The 5 wt%CQDs/BiOCl composite displayed the highest photocatalytic N_(2)reduction performance to yield NH_3(346.25μmol/(g h)),which is significantly higher than those of 3 wt%CQDs/BiOCl(256.04μmol/(g h)),7 wt%CQDs/BiOCl(254.07μmol/(g h)),and bare BiOCl(240.19μmol/(g h)).Our systematic characterizations revealed that the key role of CQDs in improving photocatalytic performance is due to their increased light harvesting capacity,remarkable electron transfer ability,and higher photocatalytic activity sites.展开更多
Many photocatalytic reactions such as CO2 reduction and N2 fixation are often limited by the activation of some key molecules. Defects in solid materials can robustly introduce coordinately unsaturated sites to serve ...Many photocatalytic reactions such as CO2 reduction and N2 fixation are often limited by the activation of some key molecules. Defects in solid materials can robustly introduce coordinately unsaturated sites to serve as highly active sites for molecular chemisorption and activation. As a result, rational defect engineering has endowed a versatile approach to further develop photocatalytic applications beyond water splitting. The subtly designed defects in photocatalysts can play critical and decisive roles in molecular activation as proven in recent years. The defects cannot only serve as active sites for molecular chemisorption, but also spatially supply channels for energy and electron transfer. In this review, we aim to summarize the diversiform photocatalytic applications using defects as active sites, including but not limited to CO2 reduction, O2 activation,H2O dissociation, N2 fixation as well as activation of other molecules. In particular, we emphatically outline how the parameters of defects (e.g.,concentration,location,geometric and electronic structures) can serve as the knobs for maneuvering molecular adsorption and activation as well as altering subsequent reaction pathway. Moreover, we underline the remaining challenges at the current stage and the potential development in the future.It is anticipated that this review consolidates the in-depth understanding towards the structure-activity relationship between defects and related reactions.展开更多
Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and i...Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and intermediate stabilization. It is imperative to elucidate the mechanism for such an influence towards the rational design of efficient catalysts;however, the complex interactions between the multiple factors involved in the system make it challenging to establish a clear structure–performance relationship. In this work, we chose ion-intercalated silver(I)-based coordination networks(AgCNs) with a well-defined structure as a model platform, which enables us to understand the regulation mechanism of counterions as the counterions are the only tuning factor involved in such a system. We prepared two isostructural Ag CNs with different intercalation ions or counterions of BF_(4)^(-) and ClO_(4)^(-)(named as AgCNs-BF_(4) and AgCNs-ClO_(4)) and found that the former has a more competitive CO_(2) electroreduction performance than the latter. AgCNs-BF_(4) achieves the highest Faradaic efficiency for CO_(2) to CO of 87.1% at-1.0 V(vs. RHE) with a higher partial current density, while AgCNs-ClO_(4) exhibits only 77.2% at the same applied potential.Spectroscopic characterizations and theoretical calculation reveal that the presence of BF_(4)^(-)is more favorable for stabilizing the COOH^(*) intermediate by weakening hydrogen bonds, which accounts for the superior activity of Ag CNs-BF_(4).展开更多
Homogenous molecular photocatalysts for CO_(2)reduction,especially metal complex-based photosensitizer-catalyst assemblages,have been attracting extensive research interests due to their efficiency and customizability...Homogenous molecular photocatalysts for CO_(2)reduction,especially metal complex-based photosensitizer-catalyst assemblages,have been attracting extensive research interests due to their efficiency and customizability.However,their low durability and recyclability limit practical applications.In this work,we immobilized the catalysts of metal terpyridyl complexes and the photosensitizer of[Ru(bpy)3]Cl2onto the surface of carbon nanotubes through covalent bonds and electrostatic interactions,respectively,transforming the homogeneous system into a heterogeneous one.Our characterizations prove that these metal complexes are well dispersed on CNTs with a high loading(ca.12 wt.%).Photocatalytic measurements reveal that catalytic activity is remarkably enhanced when the molecular catalysts are anchored,which is three times higher than that of homogeneous molecular catalysts.Moreover,when the photosensitizer of[Ru(bpy)3]Cl2is immobilized,the side reaction of hydrogen evolution is completely suppressed and the selectivity for CO production reaches 100%,with its durability also significantly improved.This work provides an effective pathway for constructing heterogeneous photocatalysts based on rational assembly of efficient molecular photosensitizers and catalysts.展开更多
Hydrogen economy,which proposes employing hydrogen to replace or supplement the current fossil-fuel-based energy economy system,is widely accepted as the future energy scheme for the sustainable and green development ...Hydrogen economy,which proposes employing hydrogen to replace or supplement the current fossil-fuel-based energy economy system,is widely accepted as the future energy scheme for the sustainable and green development of human society.While the hydrogen economy has shown tremendous potential,the associated challenges with hydrogen production and storage remain significant barriers to wide applications.In light of this consideration,the integration of green hydrogen production and storage through electrocatalysis for direct production of chemical hydrogen storage media has emerged as a potential solution to these challenges.Specifically,through electrocatalysis,CO_(2) and H_(2)O can be converted into methanol or formic acid,while N_(2) or NOx along with H_(2)O can be transformed into ammonia,streamlining the hydrogen economy scheme.In this Perspective,we provide an overview of recent developments in this technology.Additionally,we briefly discuss the general properties and corresponding production strategies via the electrolysis of these chemical hydrogen storage media.Finally,we conclude by offering insights into future perspectives in this field,anticipating that the successful advancement of such technology will propel the development of the hydrogen economy toward practical implementation.展开更多
Cu-based electrocatalysts have provoked much attention for their high activity and selectivity in carbon dioxide(CO_(2))conversion into multi-carbon hydrocarbons.However,during the electrochemical reaction,Cu catalyst...Cu-based electrocatalysts have provoked much attention for their high activity and selectivity in carbon dioxide(CO_(2))conversion into multi-carbon hydrocarbons.However,during the electrochemical reaction,Cu catalysts inevitably undergo surface reconstruction whose impact on CO_(2)conversion performance remains contentious.Here we report that polycrystalline Cu nanoparticles(denoted as Cu-s)with rich high-index facets,derived from Cu_(2−x)S through desulphurization and surface reconstruction,offer an excellent platform for investigating the role of surface reconstruction in electrocatalytic CO_(2)conversion.During the formation of Cu-s catalyst,the two stages of desulphurization and surface reconstruction can be clearly resolved by in situ X-ray absorption spectroscopy and OH−adsorption characterizations,which are well correlated with the changes in electrocatalytic performance.It turns out that the high CO_(2)conversion performance,achieved by the Cu-s catalyst(Faradic efficiency of 68.6%and partial current density of 40.8 mA/cm^(2)in H-cell toward C_(2)H_(4)production),is attributed to the increased percentage of high-index facets in Cu-s during the surface reconstruction.Furthermore,the operando electrochemical Raman spectroscopy further reveals that the conversion of the CO_(2)into the C_(2)H_(4)on Cu-s is intermediated by the production of*COCHO.Our findings manifest that the surface reconstruction is an effective method for tuning the reaction intermediate of the CO_(2)conversion toward high-value multicarbon(C2+)chemicals,and highlight the significance of in situ characterizations in enhancing the understanding of the surface structure and its role in electrocatalysis.展开更多
Sodium-ion batteries(SIBs)are considered the most up-and-coming complements for large-scale energy storage devices due to the abundance and cheap sodium.However,due to the bigger radius,it is still a great challenge t...Sodium-ion batteries(SIBs)are considered the most up-and-coming complements for large-scale energy storage devices due to the abundance and cheap sodium.However,due to the bigger radius,it is still a great challenge to develop anode materials with suitable space for the intercalation of sodium ions.Herein,we present hard carbon microtubes(HCTs)with tunable apertures derived from low-cost natural kapok fibers via a carbonization process for SIBs.The resulted HCTs feature with smaller surface area and shorter Na+diffusion path benefitting from their unique micro-nano structure.Most importantly,the wall thickness of HCTs could be regulated and controlled by the carbonization temperature.At a high temperature of 1,600℃,the carbonized HCTs possess the smallest wall thickness,which reduces the diffusion barrier of Na+and enhances the reversibility Na+storage.As a result,the 1600HCTs deliver a high initial Coulombic efficiency of 90%,good cycling stability(89.4%of capacity retention over 100 cycles at 100 mA·g^(−1)),and excellent rate capacity.This work not only charts a new path for preparing hard carbon materials with adequate ion channels and novel tubular micro-nano structures but also unravels the mechanism of hard carbon materials for sodium storage.展开更多
Synergistically combining biological whole-cell bacteria with man-made semiconductor materials innovates the way for sustainable solar-driven CO_(2)fixation,showing great promise to break through the bottleneck in tra...Synergistically combining biological whole-cell bacteria with man-made semiconductor materials innovates the way for sustainable solar-driven CO_(2)fixation,showing great promise to break through the bottleneck in traditional chemical photocatalyst systems.However,most of the biohybrids require uneconomical organic nutrients and anaerobic conditions for the successful cultivation of the bacteria to sustain the CO_(2)fixation,which severely limits their economic viability and applicability for practical application.Herein,we present an inorganic-biological hybrid system composed of obligate autotrophic bacteria Thiobacillus thioparus(T.thioparus)and CdS nanoparticles(NPs)biologically precipitated on the bacterial surface,which can achieve efficient CO_(2)fixation based entirely on cost-effective inorganic salts and without the restriction of anaerobic conditions.The optimized interface between CdS NPs and T.thioparus formed by biological precipitation plays an essential role for T.thioparus efficiently receiving photogenerated electrons from CdS NPs and thus changing the autotrophic way from chemoautotroph to photoautotroph.As a result,the CdS-T.thioparus biohybrid realizes the solar-driven CO_(2)fixation to produce multi-carbon glutamate synthase and biomass under visible-light irradiation with CO_(2)as the only carbon source.This work provides significant inspiration for the further exploration of the solar-driven self-replicating biocatalytic system to achieve CO_(2)fixation and conversion.展开更多
Electrochemical C–N coupling has generated intense research interest as a promising approach to reduce carbon and nitrogen emissions and store excess renewable electricity in valuable chemicals(e.g.,urea,amides,and a...Electrochemical C–N coupling has generated intense research interest as a promising approach to reduce carbon and nitrogen emissions and store excess renewable electricity in valuable chemicals(e.g.,urea,amides,and amines).In this review,we discuss the emerging trends in electrocatalytic C–N coupling reactions using CO_(2) and inorganic nitrogenous species(i.e.,dinitrogen(N_(2))),nitrate(NO_(2)^(-)),nitrite(NO_(3)^(-)),and ammonia(NH_(3))as raw materials.The related reaction mechanisms and potential design principles for advanced electrocatalysts are outlined.In addition,the effects of different reactors,including H-cells,membrane-based flow reactors,and membrane electrode assembly electrolyzers,on the coupling reactions are emphasized.Finally,the current challenges and future opportunities in this field are described.We aim to provide an up-to-date overview of the electrochemical C–N coupling system to advance progress toward its practical application.展开更多
The thermodynamically favorable electrocatalytic oxidation coupled with hydrogen evolution reaction(HER)is considered as a sustainable and promising technique.Nonetheless,it remains a great challenge due to the lack o...The thermodynamically favorable electrocatalytic oxidation coupled with hydrogen evolution reaction(HER)is considered as a sustainable and promising technique.Nonetheless,it remains a great challenge due to the lack of simple,cheap,highefficient electrocatalysts.Here,we successfully develop a simple and scalable electro-deposition and subsequent phosphorization route to fabricate Ni-doped Co_(2)P(Ni-Co_(2)P)nanosheets catalyst using the in-situ released Ni species from defective Ni foam as metal source.Impressively,the as-synthesized Ni-Co_(2)P catalyst exhibits excellent electrochemical 5-hydroxymethylfurfural oxidation reaction(HOR)performance with>99%2,5-furandicarboxylic acid yield and>97%Faradaic efficiency at an ultralow potential of 1.29 V vs.reversible hydrogen electrode(RHE).Experimental characterization and theoretical calculation reveal that the atomically doped Ni species can enhance the adsorption of reactant and thus lower the reaction energy barriers.By coupling the electrocatalytic HOR with HER,the employed two-electrode system using Ni-Co_(2)P and commercial Ni foam as anode and cathode,respectively,exhibits a low cell voltage of 1.53 V to drive a current density of 10 mA·cm^(−2),which is 90 mV lower than that of pure water splitting.This work provides a facile and efficient approach for the preparation of high-performance earth-abundant electrocatalysts toward the concurrent production of H_(2)and value-added chemicals.展开更多
The electricity-driven water splitting acts as a promising pathway for renewable energy conversion and storage, yet anodic oxygen evolution reaction(OER) largely hinders its efficiency. Seeking the alternatives to OER...The electricity-driven water splitting acts as a promising pathway for renewable energy conversion and storage, yet anodic oxygen evolution reaction(OER) largely hinders its efficiency. Seeking the alternatives to OER exhibits the competitive advance to address this predicament. In this work, we show a more thermodynamically and kinetically favorable reaction, electrochemical oxidative dehydrogenation(EODH)of benzylamine to replace the conventional OER, catalyzed by a cobalt cyclotetraphosphate(Co_(2)P_(4)O_(12)) nanorods catalyst grown on nickel foam. This anodic reaction lowers the electricity input of 317 mV toward the desired current density of 100 mA/cm^(2), together with a highly selective benzonitrile product of more than 97%. More specifically, when coupling it with cathodic hydrogen evolution reaction(HER),the proposed HER||benzylamine-EODH configuration only requires a cell voltage of 1.47 V@100 mA/cm^(2),exhibiting an energy-saving up to 17% relative to conventional water splitting, as well as the near unit selectivity toward cathodic H_(2) and anodic benzonitrile products.展开更多
Photocatalytic nonoxidative coupling of CH_(4)to multicarbon(C^(2+))hydrocarbons(e.g.,C,H4)and H,under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource.However,as t...Photocatalytic nonoxidative coupling of CH_(4)to multicarbon(C^(2+))hydrocarbons(e.g.,C,H4)and H,under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource.However,as the methyl intermediates prefer to undergo self-coupling to produce ethane,it is a challenging task to control the selective conversion of CH to higher valueadded CH4.Herein,we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO_(3)nanosheets for synergizing the adsorption,activation,and dehydrogenation processes in CH_(4)to C_(2)H_(4)conversion.Benefiting from the synergy,our model catalyst achieves a remarkable C^(2+)compounds yield of 31.85μmolgh with an exceptionally high C,H4 selectivity of 75.3%and a stoichiometric H_(2)evolution.In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH_(4)molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen,while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C_(2)H_(4)and suppress overoxidation.This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH_(4)to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions.展开更多
Formic acid oxidation is an important electrocatalytic reaction in proton- exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have deve...Formic acid oxidation is an important electrocatalytic reaction in proton- exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCO0* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/ activation towards improved electrocatalytic performance.展开更多
The energy crisis and global warming become severe issues. Solar-driven CO2 reduction provides a promising route to confront the predicaments, which has received much attention. The photoelectrochemical(PEC) process...The energy crisis and global warming become severe issues. Solar-driven CO2 reduction provides a promising route to confront the predicaments, which has received much attention. The photoelectrochemical(PEC) process,which can integrate the merits of both photocatalysis and electrocatalysis, boosts splendid talent for CO2 reduction with high efficiency and excellent selectivity. Recent several decades have witnessed the overwhelming development of PEC CO2 reduction. In this review, we attempt to systematically summarize the recent advanced design for PEC CO2 reduction. On account of basic principles and evaluation parameters, we firstly highlight the subtle construction for photocathodes to enhance the efficiency and selectivity of CO2 reduction, which includes the strategies for improving light utilization, supplying catalytic active sites and steering reaction pathway.Furthermore, diversiform novel PEC setups are also outlined.These exploited setups endow a bright window to surmount the intrinsic disadvantages of photocathode, showing promising potentials for future applications. Finally, we underline the challenges and key factors for the further development of PEC CO2 reduction that would enable more efficient designs for setups and deepen systematic understanding for mechanisms.展开更多
Porous materials have attracted great attention in energy and environment applications,such as metal organic frameworks(MOFs),metal aerogels,carbon aerogels,porous metal oxides.These materials could be also hybridized...Porous materials have attracted great attention in energy and environment applications,such as metal organic frameworks(MOFs),metal aerogels,carbon aerogels,porous metal oxides.These materials could be also hybridized with other materials into functional composites with superior properties.The high specific area of porous materials offer them the advantage as hosts to conduct catalytic and electrochemical reactions.On one hand,catalytic reactions include photocatalytic,p ho toe lectrocatalytic and electrocatalytic reactions over some gases.On the other hand,they can be used as electrodes in various batteries,such as alkaline metal ion batteries and electrochemical capacitors.So far,both catalysis and batteries are extremely attractive topics.There are also many obstacles to overcome in the exploration of these porous materials.The research related to porous materials for energy and environment applications is at extremely active stage,and this has motivated us to contribute with a roadmap on ’porous materials for energy and environment applications’.展开更多
Photocatalytic reduction of CO2 into high value-added CH4 is a promising solution for energy and environmental crises. Integrating semiconductors with cocatalysts can improve the activities for photocatalytic CO2 redu...Photocatalytic reduction of CO2 into high value-added CH4 is a promising solution for energy and environmental crises. Integrating semiconductors with cocatalysts can improve the activities for photocatalytic CO2 reduction; however, most metal cocatalysts mainly produce CO and H2. Herein, we report a cocatalyst hydridation approach for significantly enhancing the photocatalytic reduction of CO2 into CH4. Hydriding Pd cocatalysts into PdH0.43 played a dual role in performance enhancement. As revealed by our isotopic labeling experiments, the PdH0.43 hydride cocatalysts reduced H2 evolution, which suppressed the H2 production and facilitated the conversion of the CO intermediate into the final product: CH4. Meanwhile, hydridation promoted the electron trapping on the cocatalysts, improving the charge separation. This approach increased the photocatalytic selectivity in CH4 production from 3.2% to 63.6% on Pd{100} and from 15.6% to 73.4% on Pd{111}. The results provide insights into photocatalytic mechanism studies and introduce new opportunities for designing materials towards photocatalytic CO2 conversion.展开更多
Anodic urea oxidation reaction(UOR)is an intriguing half reaction that can replace oxygen evolution reaction(OER)and work together with hydrogen evolution reaction(HER)toward simultaneous hydrogen fuel generation and ...Anodic urea oxidation reaction(UOR)is an intriguing half reaction that can replace oxygen evolution reaction(OER)and work together with hydrogen evolution reaction(HER)toward simultaneous hydrogen fuel generation and urea-rich wastewater purification;however,it remains a challenge to achieve overall urea electrolysis with high efficiency.Herein,we report a multifunctional electrocatalyst termed as Rh/Ni V-LDH,through integration of nickel-vanadium layered double hydroxide(LDH)with rhodium single-atom catalyst(SAC),to achieve this goal.The electrocatalyst delivers high HER mass activity of0.262 A mg^(-1) and exceptionally high turnover frequency(TOF)of 2.125 s^(-1) at an overpotential of100 m V.Moreover,exceptional activity toward urea oxidation is addressed,which requires a potential of 1.33 V to yield 10 mA cm^(-2),endorsing the potential to surmount the sluggish OER.The splendid catalytic activity is enabled by the synergy of the Ni V-LDH support and the atomically dispersed Rh sites(located on the Ni-V hollow sites)as evidenced both experimentally and theoretically.The selfsupported Rh/Ni V-LDH catalyst serving as the anode and cathode for overall urea electrolysis(1 mol L^(-1) KOH with 0.33 mol L^(-1) urea as electrolyte)only requires a small voltage of 1.47 V to deliver 100 mA cm^(-2) with excellent stability.This work provides important insights into multifunctional SAC design from the perspective of support sites toward overall electrolysis applications.展开更多
Crystal phase engineering on photocatalytic materials is a subfield of photocatalysis with intensive research,which has been proven as a:versatile approach to maneuver their performance for applications in energy-and ...Crystal phase engineering on photocatalytic materials is a subfield of photocatalysis with intensive research,which has been proven as a:versatile approach to maneuver their performance for applications in energy-and environment-related fields.In this article,the state-of-the-art progress on phase-e ngin eered photocatalytic materials is reviewed.Firstly,we discuss the phase engin eeri ng on pristi ne semic on ductor photocatalysts,in which the phase-dependent light absorption,charge transfer and separation,and surface reaction behaviors in photocatalytic processes are summarized,respectively.Based on the elucidated mechanisms,the implementation of phase junctions in photocatalytic reactions is then presented.As a focus,we highlight the rational design of phase junctions toward steering the charge kinetics for enhanced photocatalytic and photoelectrocatalytic performance.Moreover,the crystal phase engineering on semiconductor-based hybrid photocatalysts is also in troduced,which un derli nes the importa nee of choosi ng a suitable phase for semic on ductor comp orients and co-catalysts as well as the synergism of differe nt semico nductor phases for improved photocatalytic performa nee.Fin ally,the challe nges and perspectives in this research field are proposed.In this review,particular emphasis is placed on establishing a linkage between crystal phase and photocatalytic activity to develop a structure-activity guide.Based on the guide,a framework is suggested for future research on the rational phase design of photocatalysts for improved performance in energy and environmental applications.展开更多
Developing carbon-based electrocatalysts with excellent N2 adsorption and activation capability holds the key to achieve highly efficient nitrogen reduction reaction(NRR)for reaching its practical application.Here,we ...Developing carbon-based electrocatalysts with excellent N2 adsorption and activation capability holds the key to achieve highly efficient nitrogen reduction reaction(NRR)for reaching its practical application.Here,we report a highly active electrocatalyst--metal-free pyrrolic-N dominated N,S co-doped carbon(pyrr-NSC)for NRR.Based on theoretical and experimental results,it is confirmed that the N and S-dopants practice a working-in-tandem mechanism on pyrr-NSC,where the N-dopants are utilized to create electropositive C sites for enhancing N2 adsorption and the S-dopants are employed to induce electron backdonation for facilitating N2 activation.The synergistic effect of the pyrrolic-N and S-dopants can also suppress the irritating hydrogen evolution reaction,further boosting the NRR performance.This work gives an indication that the combination of two different dopants on electrocatalyst can enhance NRR performance by working in the two tandem steps-the adsorption and activation of N2 molecules,providing a new strategy for NRR electrocatalyst design.展开更多
基金financially suppor ted by Key Research and Development Project of Anhui Province(No.2023h11020002)Natural Science Research Project for Universities in Anhui Province(No.KJ2021ZD0006)+3 种基金Natural Science Foundation of Anhui Province(No.2208085MB21)Fundamental Research Funds for the Central Universities of China(No.PA2022GDSK0056)Anhui Laboratory of Molecule-Based Materials(No.fzj22009)National Natural Science Foundation of China(Nos.21725102,22205108)。
文摘Over the past few decades,photocatalysis technology has received extensive attention because of its potential to mitigate or solve energy and environmental pollution problems.Designing novel materials with outstanding photocatalytic activities has become a research hotspot in this field.In this study,we prepared a series of photocatalysts in which BiOCl nanosheets were modified with carbon quantum dots(CQDs)to form CQDs/BiOCl composites by using a simple solvothermal method.The photocatalytic performance of the resulting CQDs/BiOCl composite photocatalysts was assessed by rhodamine B and tetracycline degradation under visible-light irradiation.Compared with bare BiOCl,the photocatalytic activity of the CQDs/BiOCl composites was significantly enhanced,and the 5 wt%CQDs/BiOCl composite exhibited the highest photocatalytic activity with a degradation efficiency of 94.5%after 30 min of irradiation.Moreover,photocatalytic N_(2)reduction performance was significantly improved after introducing CQDs.The 5 wt%CQDs/BiOCl composite displayed the highest photocatalytic N_(2)reduction performance to yield NH_3(346.25μmol/(g h)),which is significantly higher than those of 3 wt%CQDs/BiOCl(256.04μmol/(g h)),7 wt%CQDs/BiOCl(254.07μmol/(g h)),and bare BiOCl(240.19μmol/(g h)).Our systematic characterizations revealed that the key role of CQDs in improving photocatalytic performance is due to their increased light harvesting capacity,remarkable electron transfer ability,and higher photocatalytic activity sites.
基金financially supported in part by the National Key R&D Program of China (2017YFA0207301)NSFC (21725102, 21471141, U1532135, 21703220)+2 种基金CAS Key Research Program of Frontier Sciences (QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Team, Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (2016FXCX003)Anhui Provincial Natural Science Foundation (1708085QB26)
文摘Many photocatalytic reactions such as CO2 reduction and N2 fixation are often limited by the activation of some key molecules. Defects in solid materials can robustly introduce coordinately unsaturated sites to serve as highly active sites for molecular chemisorption and activation. As a result, rational defect engineering has endowed a versatile approach to further develop photocatalytic applications beyond water splitting. The subtly designed defects in photocatalysts can play critical and decisive roles in molecular activation as proven in recent years. The defects cannot only serve as active sites for molecular chemisorption, but also spatially supply channels for energy and electron transfer. In this review, we aim to summarize the diversiform photocatalytic applications using defects as active sites, including but not limited to CO2 reduction, O2 activation,H2O dissociation, N2 fixation as well as activation of other molecules. In particular, we emphatically outline how the parameters of defects (e.g.,concentration,location,geometric and electronic structures) can serve as the knobs for maneuvering molecular adsorption and activation as well as altering subsequent reaction pathway. Moreover, we underline the remaining challenges at the current stage and the potential development in the future.It is anticipated that this review consolidates the in-depth understanding towards the structure-activity relationship between defects and related reactions.
基金supported by financial support in part by NSFC (91961106, 51902253, 21725102)Anhui Provincial Natural Science Foundation (Grant 2108085MB46)+1 种基金Key Project of Youth Elite Support Plan in Universities of Anhui Province (Grant gxyqZD2021121)Shaanxi Provincial Natural Science Foundation (2020JQ-778)。
文摘Very recently, the local coordination environment of active sites has been found to strongly influence their performance in electrocatalytic CO_(2) reduction by tuning the intrinsic kinetics of CO_(2) activation and intermediate stabilization. It is imperative to elucidate the mechanism for such an influence towards the rational design of efficient catalysts;however, the complex interactions between the multiple factors involved in the system make it challenging to establish a clear structure–performance relationship. In this work, we chose ion-intercalated silver(I)-based coordination networks(AgCNs) with a well-defined structure as a model platform, which enables us to understand the regulation mechanism of counterions as the counterions are the only tuning factor involved in such a system. We prepared two isostructural Ag CNs with different intercalation ions or counterions of BF_(4)^(-) and ClO_(4)^(-)(named as AgCNs-BF_(4) and AgCNs-ClO_(4)) and found that the former has a more competitive CO_(2) electroreduction performance than the latter. AgCNs-BF_(4) achieves the highest Faradaic efficiency for CO_(2) to CO of 87.1% at-1.0 V(vs. RHE) with a higher partial current density, while AgCNs-ClO_(4) exhibits only 77.2% at the same applied potential.Spectroscopic characterizations and theoretical calculation reveal that the presence of BF_(4)^(-)is more favorable for stabilizing the COOH^(*) intermediate by weakening hydrogen bonds, which accounts for the superior activity of Ag CNs-BF_(4).
基金supported by the Natural Science Foundation of China(Nos.91961106,51902253 and 21725102)the Anhui Provincial Natural Science Foundation(No.2108085MB46)+1 种基金the Key Project of Youth Elite Support Plan in Universities of Anhui Province(No.gxyqZ D2021121)the Shaanxi Provincial Natural Science Foundation(No.2020JQ-778).
文摘Homogenous molecular photocatalysts for CO_(2)reduction,especially metal complex-based photosensitizer-catalyst assemblages,have been attracting extensive research interests due to their efficiency and customizability.However,their low durability and recyclability limit practical applications.In this work,we immobilized the catalysts of metal terpyridyl complexes and the photosensitizer of[Ru(bpy)3]Cl2onto the surface of carbon nanotubes through covalent bonds and electrostatic interactions,respectively,transforming the homogeneous system into a heterogeneous one.Our characterizations prove that these metal complexes are well dispersed on CNTs with a high loading(ca.12 wt.%).Photocatalytic measurements reveal that catalytic activity is remarkably enhanced when the molecular catalysts are anchored,which is three times higher than that of homogeneous molecular catalysts.Moreover,when the photosensitizer of[Ru(bpy)3]Cl2is immobilized,the side reaction of hydrogen evolution is completely suppressed and the selectivity for CO production reaches 100%,with its durability also significantly improved.This work provides an effective pathway for constructing heterogeneous photocatalysts based on rational assembly of efficient molecular photosensitizers and catalysts.
基金funded by National Key R&D Program of China(2020YFA0406103,2022YFE0126500)National Natural Science Foundation of China(21725102,22150610467,22232003)+1 种基金Strategic Priority Research Program of CAS(XDPB14)Open Funding Project of National Key Laboratory of Human Factors Engineering(SYFD062010K).
文摘Hydrogen economy,which proposes employing hydrogen to replace or supplement the current fossil-fuel-based energy economy system,is widely accepted as the future energy scheme for the sustainable and green development of human society.While the hydrogen economy has shown tremendous potential,the associated challenges with hydrogen production and storage remain significant barriers to wide applications.In light of this consideration,the integration of green hydrogen production and storage through electrocatalysis for direct production of chemical hydrogen storage media has emerged as a potential solution to these challenges.Specifically,through electrocatalysis,CO_(2) and H_(2)O can be converted into methanol or formic acid,while N_(2) or NOx along with H_(2)O can be transformed into ammonia,streamlining the hydrogen economy scheme.In this Perspective,we provide an overview of recent developments in this technology.Additionally,we briefly discuss the general properties and corresponding production strategies via the electrolysis of these chemical hydrogen storage media.Finally,we conclude by offering insights into future perspectives in this field,anticipating that the successful advancement of such technology will propel the development of the hydrogen economy toward practical implementation.
基金supported in part by the National Key R&D Program of China(Nos.2017YFA0207301 and 2017YFA0403402)the National Natural Science Foundation of China(Nos.21725102,91961106,U1832156,and 22075267)+4 种基金Science and Technological Fund of Anhui Province for Outstanding Youth(No.2008085J05)Youth Innovation Promotion Association of CAS(No.2019444)Young Elite Scientist Sponsorship Program by CAST,China Postdoctoral Science Foundation(Nos.2019M652190 and 2020T130627)Users with Excellence Program of Hefei Science Center CAS(No.2020HSC-UE003)DNL Cooperation Fund,CAS(No.DNL201922).
文摘Cu-based electrocatalysts have provoked much attention for their high activity and selectivity in carbon dioxide(CO_(2))conversion into multi-carbon hydrocarbons.However,during the electrochemical reaction,Cu catalysts inevitably undergo surface reconstruction whose impact on CO_(2)conversion performance remains contentious.Here we report that polycrystalline Cu nanoparticles(denoted as Cu-s)with rich high-index facets,derived from Cu_(2−x)S through desulphurization and surface reconstruction,offer an excellent platform for investigating the role of surface reconstruction in electrocatalytic CO_(2)conversion.During the formation of Cu-s catalyst,the two stages of desulphurization and surface reconstruction can be clearly resolved by in situ X-ray absorption spectroscopy and OH−adsorption characterizations,which are well correlated with the changes in electrocatalytic performance.It turns out that the high CO_(2)conversion performance,achieved by the Cu-s catalyst(Faradic efficiency of 68.6%and partial current density of 40.8 mA/cm^(2)in H-cell toward C_(2)H_(4)production),is attributed to the increased percentage of high-index facets in Cu-s during the surface reconstruction.Furthermore,the operando electrochemical Raman spectroscopy further reveals that the conversion of the CO_(2)into the C_(2)H_(4)on Cu-s is intermediated by the production of*COCHO.Our findings manifest that the surface reconstruction is an effective method for tuning the reaction intermediate of the CO_(2)conversion toward high-value multicarbon(C2+)chemicals,and highlight the significance of in situ characterizations in enhancing the understanding of the surface structure and its role in electrocatalysis.
基金supported by the Natural Science Research Project for Universities in Anhui Province(No.KJ2021ZD0006)the Natural Science Foundation of Anhui Province(No.2208085MB21)+3 种基金the Fundamental Research Funds for the Central Universities of China(No.PA2022GDSK0056)the University Synergy Innovation Program of Anhui Province(Nos.GXXT-2020-073 and GXXT-2020-074),the National Key R&D Program of China(No.2020YFA0406103)the National Natural Science Foundation of China(Nos.21725102,91961106,91963108,and 22175165)Singapore National Research Foundation under NRF RF Award No.Tier 12017-T1-001-075.
文摘Sodium-ion batteries(SIBs)are considered the most up-and-coming complements for large-scale energy storage devices due to the abundance and cheap sodium.However,due to the bigger radius,it is still a great challenge to develop anode materials with suitable space for the intercalation of sodium ions.Herein,we present hard carbon microtubes(HCTs)with tunable apertures derived from low-cost natural kapok fibers via a carbonization process for SIBs.The resulted HCTs feature with smaller surface area and shorter Na+diffusion path benefitting from their unique micro-nano structure.Most importantly,the wall thickness of HCTs could be regulated and controlled by the carbonization temperature.At a high temperature of 1,600℃,the carbonized HCTs possess the smallest wall thickness,which reduces the diffusion barrier of Na+and enhances the reversibility Na+storage.As a result,the 1600HCTs deliver a high initial Coulombic efficiency of 90%,good cycling stability(89.4%of capacity retention over 100 cycles at 100 mA·g^(−1)),and excellent rate capacity.This work not only charts a new path for preparing hard carbon materials with adequate ion channels and novel tubular micro-nano structures but also unravels the mechanism of hard carbon materials for sodium storage.
基金supported by the National Key R&D Program of China(No.2020YFA0406103)the National Natural Science Foundation of China(Nos.21725102,91961106,and 91963108),DNL Cooperation Fund,CAS(No.DNL201922)Youth Innovation Promotion Association CAS.
文摘Synergistically combining biological whole-cell bacteria with man-made semiconductor materials innovates the way for sustainable solar-driven CO_(2)fixation,showing great promise to break through the bottleneck in traditional chemical photocatalyst systems.However,most of the biohybrids require uneconomical organic nutrients and anaerobic conditions for the successful cultivation of the bacteria to sustain the CO_(2)fixation,which severely limits their economic viability and applicability for practical application.Herein,we present an inorganic-biological hybrid system composed of obligate autotrophic bacteria Thiobacillus thioparus(T.thioparus)and CdS nanoparticles(NPs)biologically precipitated on the bacterial surface,which can achieve efficient CO_(2)fixation based entirely on cost-effective inorganic salts and without the restriction of anaerobic conditions.The optimized interface between CdS NPs and T.thioparus formed by biological precipitation plays an essential role for T.thioparus efficiently receiving photogenerated electrons from CdS NPs and thus changing the autotrophic way from chemoautotroph to photoautotroph.As a result,the CdS-T.thioparus biohybrid realizes the solar-driven CO_(2)fixation to produce multi-carbon glutamate synthase and biomass under visible-light irradiation with CO_(2)as the only carbon source.This work provides significant inspiration for the further exploration of the solar-driven self-replicating biocatalytic system to achieve CO_(2)fixation and conversion.
基金This work was financially supported in part by the National Key R&D Program of China(2020YFA0406103)NSFC(21725102,22122506,91961106,U1832156,22105192,22075267)+4 种基金Strategic Priority Research Program of the CAS(XDPB14)the Open Funding Project of National Key Laboratory of Human Factors Engineering(SYFD062010K)Anhui Provincial Natural Science Foundation(2008085J05)Youth Innovation Promotion Association of CAS(2019444)China Post-doctoral Science Foundation(2021M693065,2021TQ0322).
文摘Electrochemical C–N coupling has generated intense research interest as a promising approach to reduce carbon and nitrogen emissions and store excess renewable electricity in valuable chemicals(e.g.,urea,amides,and amines).In this review,we discuss the emerging trends in electrocatalytic C–N coupling reactions using CO_(2) and inorganic nitrogenous species(i.e.,dinitrogen(N_(2))),nitrate(NO_(2)^(-)),nitrite(NO_(3)^(-)),and ammonia(NH_(3))as raw materials.The related reaction mechanisms and potential design principles for advanced electrocatalysts are outlined.In addition,the effects of different reactors,including H-cells,membrane-based flow reactors,and membrane electrode assembly electrolyzers,on the coupling reactions are emphasized.Finally,the current challenges and future opportunities in this field are described.We aim to provide an up-to-date overview of the electrochemical C–N coupling system to advance progress toward its practical application.
基金the National Key Research and Development(R&D)Program of China(No.2020YFA0406103)the National Natural Science Foundation of China(NSFC)(Nos.21725102,51902311,22122506,91961106,22075267,and 21803002)+5 种基金Strategic Priority Research Program of the CAS(No.XDPB14)Anhui Provincial Natural Science Foundation(No.2008085J05)Youth Innovation Promotion Association of CAS(No.2019444)Open Funding Project of National Key Laboratory of Human Factors Engineering(No.SYFD062010K)Users with Excellence Program of Hefei Science Center CAS(No.2020HSCUE003)Fundamental Research Funds for the Central Universities(No.WK2060000039).
文摘The thermodynamically favorable electrocatalytic oxidation coupled with hydrogen evolution reaction(HER)is considered as a sustainable and promising technique.Nonetheless,it remains a great challenge due to the lack of simple,cheap,highefficient electrocatalysts.Here,we successfully develop a simple and scalable electro-deposition and subsequent phosphorization route to fabricate Ni-doped Co_(2)P(Ni-Co_(2)P)nanosheets catalyst using the in-situ released Ni species from defective Ni foam as metal source.Impressively,the as-synthesized Ni-Co_(2)P catalyst exhibits excellent electrochemical 5-hydroxymethylfurfural oxidation reaction(HOR)performance with>99%2,5-furandicarboxylic acid yield and>97%Faradaic efficiency at an ultralow potential of 1.29 V vs.reversible hydrogen electrode(RHE).Experimental characterization and theoretical calculation reveal that the atomically doped Ni species can enhance the adsorption of reactant and thus lower the reaction energy barriers.By coupling the electrocatalytic HOR with HER,the employed two-electrode system using Ni-Co_(2)P and commercial Ni foam as anode and cathode,respectively,exhibits a low cell voltage of 1.53 V to drive a current density of 10 mA·cm^(−2),which is 90 mV lower than that of pure water splitting.This work provides a facile and efficient approach for the preparation of high-performance earth-abundant electrocatalysts toward the concurrent production of H_(2)and value-added chemicals.
基金financially supported in part by National Key R&D Program of China(No.2020YFA0406103)National Natural Science Foundation of China(NSFC,Nos.21725102,22122506,22075267,U1832156,91961106,51902311)+5 种基金DNL Cooperation Fund,CAS(No.DNL201922)Strategic Priority Research Program of the CAS(No.XDPB14)Anhui Provincial Natural Science Foundation(No.2008085J05)Youth Innovation Promotion Association of CAS(No.2019444)Open Funding Project of National Key Laboratory of Human Factors Engineering(No.SYFD062010K)support from USTC Center for Micro-and Nanoscale Research and Fabrication。
文摘The electricity-driven water splitting acts as a promising pathway for renewable energy conversion and storage, yet anodic oxygen evolution reaction(OER) largely hinders its efficiency. Seeking the alternatives to OER exhibits the competitive advance to address this predicament. In this work, we show a more thermodynamically and kinetically favorable reaction, electrochemical oxidative dehydrogenation(EODH)of benzylamine to replace the conventional OER, catalyzed by a cobalt cyclotetraphosphate(Co_(2)P_(4)O_(12)) nanorods catalyst grown on nickel foam. This anodic reaction lowers the electricity input of 317 mV toward the desired current density of 100 mA/cm^(2), together with a highly selective benzonitrile product of more than 97%. More specifically, when coupling it with cathodic hydrogen evolution reaction(HER),the proposed HER||benzylamine-EODH configuration only requires a cell voltage of 1.47 V@100 mA/cm^(2),exhibiting an energy-saving up to 17% relative to conventional water splitting, as well as the near unit selectivity toward cathodic H_(2) and anodic benzonitrile products.
基金supported by the National Key R&D Program of China(2020YFA0406103)the National Natural Science Foundation of China(22232003,21725102,91961106,91963108,22175165,and 51902253)+5 种基金the DNL Cooperation Fund,the CAS(DNL201922)the Strategic Priority Research Program of the CAS(XDPB14)the Open Funding Project of National Key Laboratory of Human Factors Engineering(No.SYFD062010K)the Youth Innovation Promotion Association CAS(2021451),the Natural Science Foundation of Shaanxi Province(2020JQ-778)the USTC Research Funds of the Double First-Class Initiative(YD2060002020)the Fundamental Research Funds for Central Universities of the Central South University(WK2400000004)。
文摘Photocatalytic nonoxidative coupling of CH_(4)to multicarbon(C^(2+))hydrocarbons(e.g.,C,H4)and H,under ambient conditions provides a promising energy-conserving approach for utilization of carbon resource.However,as the methyl intermediates prefer to undergo self-coupling to produce ethane,it is a challenging task to control the selective conversion of CH to higher valueadded CH4.Herein,we adopt a synergistic catalysis strategy by integrating Pd-Zn active sites on visible light-responsive defective WO_(3)nanosheets for synergizing the adsorption,activation,and dehydrogenation processes in CH_(4)to C_(2)H_(4)conversion.Benefiting from the synergy,our model catalyst achieves a remarkable C^(2+)compounds yield of 31.85μmolgh with an exceptionally high C,H4 selectivity of 75.3%and a stoichiometric H_(2)evolution.In situ spectroscopic studies reveal that the Zn sites promote the adsorption and activation of CH_(4)molecules to generate methyl and methoxy intermediates with the assistance of lattice oxygen,while the Pd sites facilitate the dehydrogenation of methoxy to methylene radicals for producing C_(2)H_(4)and suppress overoxidation.This work demonstrates a strategy for designing efficient photocatalysts toward selective coupling of CH_(4)to higher value-added chemicals and highlights the importance of synergistic active sites to the synergy of key steps in catalytic reactions.
文摘Formic acid oxidation is an important electrocatalytic reaction in proton- exchange membrane (PEM) fuel cells, in which both active sites and species adsorption/activation play key roles. In this study, we have developed hollow Pd-Ag alloy nanostructures with high active surface areas for application to electrocatalytic formic acid oxidation. When a certain amount of Ag is incorporated into a Pd lattice, which is already a highly active material for formic acid oxidation, the electrocatalytic activity can be significantly boosted. As indicated by theoretical simulations, coupling between Pd and Ag induces polarization charges on Pd catalytic sites, which can enhance the adsorption of HCO0* species. As a result, the designed electrocatalysts can achieve reduced Pd usage and enhanced catalytic properties at the same time. This study represents an approach that simultaneously fabricates hollow structures to increase the number of active sites and utilizes interatomic interactions to tune species adsorption/ activation towards improved electrocatalytic performance.
基金financially supported in part by the National Key R&D Program of China (2017YFA0207301)the National Basic Research Program of China (973 Program, 2014CB848900)+5 种基金the National Natural Science Foundation of China (21471141 and U1532135)the CAS Key Research Program of Frontier Sciences (QYZDB-SSW-SLH018)the CAS Interdisciplinary Innovation Team, the Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology (2016FXCX003)the Recruitment Program of Global Experts, the CAS Hundred Talent Program, Anhui Provincial Natural Science Foundation (1708085QB26)China Postdoctoral Science Foundation (BH2060000034)the Fundamental Research Funds for the Central Universities (WK2060190064)
文摘The energy crisis and global warming become severe issues. Solar-driven CO2 reduction provides a promising route to confront the predicaments, which has received much attention. The photoelectrochemical(PEC) process,which can integrate the merits of both photocatalysis and electrocatalysis, boosts splendid talent for CO2 reduction with high efficiency and excellent selectivity. Recent several decades have witnessed the overwhelming development of PEC CO2 reduction. In this review, we attempt to systematically summarize the recent advanced design for PEC CO2 reduction. On account of basic principles and evaluation parameters, we firstly highlight the subtle construction for photocathodes to enhance the efficiency and selectivity of CO2 reduction, which includes the strategies for improving light utilization, supplying catalytic active sites and steering reaction pathway.Furthermore, diversiform novel PEC setups are also outlined.These exploited setups endow a bright window to surmount the intrinsic disadvantages of photocathode, showing promising potentials for future applications. Finally, we underline the challenges and key factors for the further development of PEC CO2 reduction that would enable more efficient designs for setups and deepen systematic understanding for mechanisms.
基金financially support by an Australian Research Council (ARC) Discovery Project (No. DP200100965)a Griffith University Postdoctoral Fellowship
文摘Porous materials have attracted great attention in energy and environment applications,such as metal organic frameworks(MOFs),metal aerogels,carbon aerogels,porous metal oxides.These materials could be also hybridized with other materials into functional composites with superior properties.The high specific area of porous materials offer them the advantage as hosts to conduct catalytic and electrochemical reactions.On one hand,catalytic reactions include photocatalytic,p ho toe lectrocatalytic and electrocatalytic reactions over some gases.On the other hand,they can be used as electrodes in various batteries,such as alkaline metal ion batteries and electrochemical capacitors.So far,both catalysis and batteries are extremely attractive topics.There are also many obstacles to overcome in the exploration of these porous materials.The research related to porous materials for energy and environment applications is at extremely active stage,and this has motivated us to contribute with a roadmap on ’porous materials for energy and environment applications’.
基金Acknowledgements This work was financially supported in part by the National Natural Science Foundation of China (Nos. 21471141, U1532135, and 21603191), CAS Key Research Program of Frontier Sciences (No. QYZDB- SSW-SLH018), Zhejiang Provincial Natural Science Foundation (No. LQ16B010001), Recruitment Program of Global Experts, and CAS Hundred Talent Program XAFS measurements were performed at the beamline BL14W1 in the Shanghai Synchrotron Radiation Facility (SSRF), China.
文摘Photocatalytic reduction of CO2 into high value-added CH4 is a promising solution for energy and environmental crises. Integrating semiconductors with cocatalysts can improve the activities for photocatalytic CO2 reduction; however, most metal cocatalysts mainly produce CO and H2. Herein, we report a cocatalyst hydridation approach for significantly enhancing the photocatalytic reduction of CO2 into CH4. Hydriding Pd cocatalysts into PdH0.43 played a dual role in performance enhancement. As revealed by our isotopic labeling experiments, the PdH0.43 hydride cocatalysts reduced H2 evolution, which suppressed the H2 production and facilitated the conversion of the CO intermediate into the final product: CH4. Meanwhile, hydridation promoted the electron trapping on the cocatalysts, improving the charge separation. This approach increased the photocatalytic selectivity in CH4 production from 3.2% to 63.6% on Pd{100} and from 15.6% to 73.4% on Pd{111}. The results provide insights into photocatalytic mechanism studies and introduce new opportunities for designing materials towards photocatalytic CO2 conversion.
基金finically supported by the National Key R&D Program of China(2017YFE0120500)the National Natural Science Foundation of China(51972129,51702150,and 21725102)+2 种基金the Key Research and Development Program of Hubei(2020BAB079)Bintuan Science and Technology Program(2020DB002,and 2022DB009)the Science and Technology Innovation Committee Foundation of Shenzhen(JCYJ20210324141613032 and JCYJ20190809142019365)。
文摘Anodic urea oxidation reaction(UOR)is an intriguing half reaction that can replace oxygen evolution reaction(OER)and work together with hydrogen evolution reaction(HER)toward simultaneous hydrogen fuel generation and urea-rich wastewater purification;however,it remains a challenge to achieve overall urea electrolysis with high efficiency.Herein,we report a multifunctional electrocatalyst termed as Rh/Ni V-LDH,through integration of nickel-vanadium layered double hydroxide(LDH)with rhodium single-atom catalyst(SAC),to achieve this goal.The electrocatalyst delivers high HER mass activity of0.262 A mg^(-1) and exceptionally high turnover frequency(TOF)of 2.125 s^(-1) at an overpotential of100 m V.Moreover,exceptional activity toward urea oxidation is addressed,which requires a potential of 1.33 V to yield 10 mA cm^(-2),endorsing the potential to surmount the sluggish OER.The splendid catalytic activity is enabled by the synergy of the Ni V-LDH support and the atomically dispersed Rh sites(located on the Ni-V hollow sites)as evidenced both experimentally and theoretically.The selfsupported Rh/Ni V-LDH catalyst serving as the anode and cathode for overall urea electrolysis(1 mol L^(-1) KOH with 0.33 mol L^(-1) urea as electrolyte)only requires a small voltage of 1.47 V to deliver 100 mA cm^(-2) with excellent stability.This work provides important insights into multifunctional SAC design from the perspective of support sites toward overall electrolysis applications.
基金This work was financially supported in part by the National Key R&D Program of China(No.2017YFA0207301)the National Natural Science Foundation of China(Nos.21725102,21471141,21603191,and U1532135)+1 种基金CAS Key Research Program of Frontier Sciences(No.QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Team,and Innovative Program of Development Foundation of Hefei Center for Physical Science and Technology(No.2016FXCX003).
文摘Crystal phase engineering on photocatalytic materials is a subfield of photocatalysis with intensive research,which has been proven as a:versatile approach to maneuver their performance for applications in energy-and environment-related fields.In this article,the state-of-the-art progress on phase-e ngin eered photocatalytic materials is reviewed.Firstly,we discuss the phase engin eeri ng on pristi ne semic on ductor photocatalysts,in which the phase-dependent light absorption,charge transfer and separation,and surface reaction behaviors in photocatalytic processes are summarized,respectively.Based on the elucidated mechanisms,the implementation of phase junctions in photocatalytic reactions is then presented.As a focus,we highlight the rational design of phase junctions toward steering the charge kinetics for enhanced photocatalytic and photoelectrocatalytic performance.Moreover,the crystal phase engineering on semiconductor-based hybrid photocatalysts is also in troduced,which un derli nes the importa nee of choosi ng a suitable phase for semic on ductor comp orients and co-catalysts as well as the synergism of differe nt semico nductor phases for improved photocatalytic performa nee.Fin ally,the challe nges and perspectives in this research field are proposed.In this review,particular emphasis is placed on establishing a linkage between crystal phase and photocatalytic activity to develop a structure-activity guide.Based on the guide,a framework is suggested for future research on the rational phase design of photocatalysts for improved performance in energy and environmental applications.
基金financially supported in part by the National Key R&D Program of China(No.2017YFA0207301)the National Natural Science Foundation of China(Nos.21725102,U1832156,91961106,22075267,and 21950410514)+5 种基金CAS Key Research Program of Frontier Sciences(No.QYZDB-SSW-SLH018)CAS Interdisciplinary Innovation Team,Science and Technological Fund of Anhui Province for Outstanding Youth(No.2008085J05)Youth Innovation Promotion Association of CAS(No.2019444)Chinese Academy of Sciences Presidents International Fellowship Initiative(Nos.2019PC0114 and 2020T130627)China Postdoctoral Science Foundation(No.2019M652190)Young Elite Scientist Sponsorship Program by CAST,and DNL Cooperation Fund,CAS(No.DNL201922).
文摘Developing carbon-based electrocatalysts with excellent N2 adsorption and activation capability holds the key to achieve highly efficient nitrogen reduction reaction(NRR)for reaching its practical application.Here,we report a highly active electrocatalyst--metal-free pyrrolic-N dominated N,S co-doped carbon(pyrr-NSC)for NRR.Based on theoretical and experimental results,it is confirmed that the N and S-dopants practice a working-in-tandem mechanism on pyrr-NSC,where the N-dopants are utilized to create electropositive C sites for enhancing N2 adsorption and the S-dopants are employed to induce electron backdonation for facilitating N2 activation.The synergistic effect of the pyrrolic-N and S-dopants can also suppress the irritating hydrogen evolution reaction,further boosting the NRR performance.This work gives an indication that the combination of two different dopants on electrocatalyst can enhance NRR performance by working in the two tandem steps-the adsorption and activation of N2 molecules,providing a new strategy for NRR electrocatalyst design.