The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor ...The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.展开更多
A core-shell type Co_(19)-added polyoxometalate H_(17)Na_(4)Cs_(21)[Co_(19)(μ_(3)-OH)_(12)(A-α-SiW_(10)O_(37))_(6)]·8 Cl·12H_(2)O(1)has been made under hydrothermal conditions guided by the lacunary direct...A core-shell type Co_(19)-added polyoxometalate H_(17)Na_(4)Cs_(21)[Co_(19)(μ_(3)-OH)_(12)(A-α-SiW_(10)O_(37))_(6)]·8 Cl·12H_(2)O(1)has been made under hydrothermal conditions guided by the lacunary directing synthetic strategy.Single crystal X-ray diffraction(SXRD)has shown that 19 Co^(2+)are arranged in a flat plane through edge sharing in a mode of 3-4-5-4-3,forming a core-shell type polyanion cluster{Co_(19)(SiW_(10))_6}with a diameter of approximately 2.24 nm.Visible-light-driven photocatalytic hydrogen evolution performance studies have shown that 1 is an efficient heterogeneous water reduction catalyst(WRC)with the H_(2)evolution rate of 2902.5μmol h^(-1)g^(-1).Moreover,the cycle tests indicated that 1 was also a good heterogeneous catalyst.展开更多
NiMo-based catalysts show significant potential for the hydrogen evolution reaction(HER).Optimizing the electronic structure and enhancing mass transfer are two critical factors for improving catalytic performance,but...NiMo-based catalysts show significant potential for the hydrogen evolution reaction(HER).Optimizing the electronic structure and enhancing mass transfer are two critical factors for improving catalytic performance,but they remain significant challenges.Herein,we present a route for synthesizing two-dimensional(2D)porous Mo_(2)N-Ni heterojunction nanosheets with tuned Ni-Mo ratio for enhanced alkaline HER performance.A precursor can be easily synthesized by assembling polyoxometalate clusters(PMo_(12))with layered hydroxy oxides(Ni(OH)_(2)).It is found that the interaction between PMo_(12)and Ni(OH)_(2)can effectively protect the particles from significant agglomeration during pyrolysis,resulting in the formation of 2D porous sheets composed of small Mo_(2)N-Ni units.The transfer of electrons from Ni to Mo_(2)N results in the redistribution of electrons at the heterojunction,optimizing the adsorption and desorption of intermediates.Moreover,the 2D porous structure comprised of small particles enhances mass transfer,thereby reducing the impedance of the catalyst.Consequently,the catalyst with an optimized Mo/Ni ratio exhibits an overpotential of 19 mV at 10 mA cm^(-2),being comparable to that of commercial Pt/C catalyst.The anion exchange membrane(AEM)electrolyzer,consisting of optimized Mo_(2)N-Ni and NiFe-LDH,achieves a current density of 500 mA cm^(-2)at 1.80 V and can operate stably for 300 h.This assembly method offers an effective strategy for the large-scale preparation of efficient catalysts.展开更多
Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparti...Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.展开更多
The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative...The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.展开更多
The hydrogen evolution reaction(HER)is crucial for hydrogen production and sustainable energy storage.Molybdenum disulfide(MoS_(2)),a representative transition metal dichalcogenides(TMDs),shows potential as an HER cat...The hydrogen evolution reaction(HER)is crucial for hydrogen production and sustainable energy storage.Molybdenum disulfide(MoS_(2)),a representative transition metal dichalcogenides(TMDs),shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects.Here,we report a salt-assisted chemical vapor deposition(CVD)method for synthesizing high-quality tungsten ditelluride(WTe_(2))with tunable morphologies using alkali halides(NaCl,KCl and LiCl).The prepared WTe_(2) nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity,with nanosheets showing superior performance.To evaluate WTe_(2) as a contact electrode,WTe_(2)−MoS_(2) heterostructures were fabricated and compared with graphene-MoS_(2) counterparts.The WTe_(2)−MoS_(2) heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at-10 mA/cm^(2),significantly outperforming graphene-based electrodes.This improvement is attributed to the excellent conductivity of WTe_(2) and reduced interfacial Schottky barriers.Moreover,we systematically investigate the influence of WTe_(2) thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure,further confirming the effectiveness of WTe_(2) as a contact electrode for enhancing the HER activity of MoS_(2).This study offers a novel approach for enhancing the HER performance of MoS_(2) through controlled WTe_(2) growth and application as a contact electrode.Our findings provide valuable insights into the synthesis of high-quality WTe_(2) and broaden the potential applications of two-dimensional materials in energy catalysis.展开更多
The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere f...The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.展开更多
Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru ...Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru has aroused significant concern because of its Pt-like activity and much lower price.However,it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance.展开更多
Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this s...Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.展开更多
The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alka...The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.展开更多
Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to thei...Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.展开更多
Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transfor...Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transformation.Herein,we demonstrate that PtFeNiCoCu high-entropy alloy(HEA)nanocrystals can act as efficient cocatalysts for H_(2)evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide(CdS)quantum dots(QDs)with uniform sizes of 4.0±0.5 nm.HEA nanocrystals were prepared via a simple solvothermal approach,and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites.The optimized HEA/CdS sample presented an enhanced photocatalytic H_(2)production rate of 7.15 mmol g^(-1)h^(-1),which was 13 times that of pure CdS QDs.Moreover,a cinnamyl alcohol conversion of 96.2%with cinnamaldehyde selectivity of 99.5%was achieved after photoreaction for 3 h.The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm.From d-band center analysis,Pt atoms in the HEA are the active sites for H_(2)evolution,exhibiting higher catalytic activity than pure Pt.Meanwhile,the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity.Moreover,femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS,which is vital for achieving enhanced photocatalytic activity.This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.展开更多
As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attra...As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.展开更多
Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a...Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.展开更多
The effects of seemingly inert alkali metal(AM)cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts ...The effects of seemingly inert alkali metal(AM)cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts in recent years.The hydrogen and oxygen evolution reactions during alkaline water electrolysis and the oxygen electro-reduction taking place in fuel cells are of particular importance.There is no universal theory explaining all the details of the AM cation effect in electrocatalysis.For example,it remains unclear how“spectator”AM-cations can change the kinetics of electrocatalytic reactions often more significantly than the modifications of the elec-trode structure and composition.This situation originates partly from a lack of systematic experimental and theoretical studies of this phenomenon.The present work exploits impedance spectroscopy to investigate the influence of the AM cations on the mechanism of the hydrogen evolution reaction at Pt microelectrodes.The activity follows the trend:Li^(+)≥Na^(+)≥K^(+)≥Cs^(+),where the highest activity corresponds to 0.1 M LiOH electrolytes at low overpotentials.We demonstrate that the nature of the AM cations also changes the relative contribution of the Volmer–Heyrovsky and Volmer–Tafel mechanisms to the overall reaction,with the former being more important for LiOH electrolytes.Our density functional theory-based thermodynamics and molecular dynamics calculations support these findings.展开更多
As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind en...As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.展开更多
Transition metal carbides,known as MXenes,particularly Ti_(3)C_(2)T_(x),have been extensively explored as promising materials for electrochemical reactions.However,transition metal carbonitride MXenes with high nitrog...Transition metal carbides,known as MXenes,particularly Ti_(3)C_(2)T_(x),have been extensively explored as promising materials for electrochemical reactions.However,transition metal carbonitride MXenes with high nitrogen content for electrochemical reactions are rarely reported.In this work,transition metal carbonitride MXenes incorporated with Pt-based electrocatalysts,ranging from single atoms to sub-nanometer dimensions,are explored for hydrogen evolution reaction(HER).The fabricated Pt clusters/MXene catalyst exhibits superior HER performance compared to the single-atom-incorporated MXene and commercial Pt/C catalyst in both acidic and alkaline electrolytes.The optimized sample shows low overpotentials of 28,65,and 154 mV at a current densities of 10,100,and 500 m A cm^(-2),a small Tafel slope of 29 m V dec^(-1),a high mass activity of 1203 mA mgPt^(-1)and an excellent turnover frequency of 6.1 s^(-1)in the acidic electrolyte.Density functional theory calculations indicate that this high performance can be attributed to the enhanced active sites,increased surface functional groups,faster charge transfer dynamics,and stronger electronic interaction between Pt and MXene,resulting in optimized hydrogen absorption/desorption toward better HER.This work demonstrates that MXenes with a high content of nitrogen may be promising candidates for various catalytic reactions by incorporating single atoms or clusters.展开更多
The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,whi...The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.展开更多
Ru-based nanomaterials have been demonstrated to be highly active electrocatalysts for hydrogen evo-lution reaction(HER),yet weak water adsorption and splitting ability in neutral media thus it is rather difficult for...Ru-based nanomaterials have been demonstrated to be highly active electrocatalysts for hydrogen evo-lution reaction(HER),yet weak water adsorption and splitting ability in neutral media thus it is rather difficult for the intermediates to adsorb on the active site.Herein,we introduce a concept of the prox-imity effect,com prising adjacent Ru and RuO_(2) nanoparticles coupled on TiO_(2)(Ru/RuO_(2)-TiO_(2)),for the synergic promotion of water molecule adsorption and splitting,significantly enhancing HER electrocatal-ysis performance.The in-situ spectroscopy experiments and density function theory(DFT)simulations demonstrated that the proximity effect between the adjacent Ru nanoparticles and RuO_(2) nanoparticles can accelerate water adsorption and splitting.As a result,the as-made Ru/RuO_(2)-TiO_(2) only need overpo-tentials of 52.7,16.0,and 16.4 mV to achieve the current density of 10 mA cm-2 in neutral,acid,and alkaline media,respectively.The mass activity of Ru/RuO_(2)-TiO_(2) in neutral media is 320 and 117 times higher than that of commercial Ru/C and Pt/C at the overpotential of 100 mV,respectively.This work emphasizes the proximity effect for activation of reactants which can be extended to other electrocat-alytic reactions.展开更多
Organic nanophotocatalysts are promising candidates for solar fuels production,but they still face the challenge of unfavorable geminate recombination due to the limited exciton diffusion lengths.Here,we introduce a b...Organic nanophotocatalysts are promising candidates for solar fuels production,but they still face the challenge of unfavorable geminate recombination due to the limited exciton diffusion lengths.Here,we introduce a binary nanophotocatalyst fabricated by blending two polymers,PS-PEG5(PS)and PBT-PEG5(PBT),with matched absorption and emission spectra,enabling a Forster resonance energy transfer(FRET)process for enhanced photocatalysis.These heterostructure nanophotocatalysts are processed using a facile and scalable flash nanoprecipitation(FNP)technique with precious kinetic control over binary nanoparticle formation.The resulting nanoparticles exhibit an exceptional photocatalytic hydrogen evolution rate up to 65 mmol g^(-1) h^(-1),2.5 times higher than that single component nanoparticles.Characterizations through fluorescence spectra and transient absorption spectra confirm the hetero-energy transfer within the binary nanoparticles,which prolongs the excited-state lifetime and extends the namely“effective exciton diffusion length”.Our finding opens new avenues for designing efficient organic photocatalysts by improving exciton migration.展开更多
文摘The efficiency and stability of catalysts for photocatalytic hydrogen evolution(PHE)are largely governed by the charge transfer behaviors across the heterojunction interfaces.In this study,CuO,a typical semiconductor featuring a broad spectral absorption range,is successfully employed as the electron acceptor to combine with CdS for constructing a S-scheme heterojunction.The optimized photocatalyst(CdSCuO2∶1)delivers an exceptional hydrogen evolution rate of 18.89 mmol/(g·h),4.15-fold higher compared with bare CdS.X-ray photoelectron spectroscopy(XPS)and ultraviolet-visible diffuse reflection absorption spectroscopy(UV-vis DRS)confirmed the S-scheme band structure of the composites.Moreover,the surface photovoltage(SPV)and electron paramagnetic resonance(EPR)indicated that the photogenerated electrons and photogenerated holes of CdS-CuO2∶1 were respectively transferred to the conduction band(CB)of CdS with a higher reduction potential and the valence band(VB)of CuO with a higher oxidation potential under illumination,as expected for the S-scheme mechanism.Density-functional-theory calculations of the electron density difference(EDD)disclose an interfacial electric field oriented from CdS to CuO.This built-in field suppresses charge recombination and accelerates carrier migration,rationalizing the markedly enhanced PHE activity.This study offers a novel strategy for designing S-scheme heterojunctions with high light harvesting and charge utilization toward sustainable solar-tohydrogen conversion.
基金supported by the National Natural Science Foundation of China(21831001,21571016,91122028)the National Science Fund for Distinguished Young Scholars(20725101)。
文摘A core-shell type Co_(19)-added polyoxometalate H_(17)Na_(4)Cs_(21)[Co_(19)(μ_(3)-OH)_(12)(A-α-SiW_(10)O_(37))_(6)]·8 Cl·12H_(2)O(1)has been made under hydrothermal conditions guided by the lacunary directing synthetic strategy.Single crystal X-ray diffraction(SXRD)has shown that 19 Co^(2+)are arranged in a flat plane through edge sharing in a mode of 3-4-5-4-3,forming a core-shell type polyanion cluster{Co_(19)(SiW_(10))_6}with a diameter of approximately 2.24 nm.Visible-light-driven photocatalytic hydrogen evolution performance studies have shown that 1 is an efficient heterogeneous water reduction catalyst(WRC)with the H_(2)evolution rate of 2902.5μmol h^(-1)g^(-1).Moreover,the cycle tests indicated that 1 was also a good heterogeneous catalyst.
基金supported by the National Key R&D Program of China(2022YFA1503002,2022YFA1503003)the National Natural Science Foundation of China(22271081)+2 种基金the Natural Science Foundation of Heilongjiang Province(PL2024B017)the Postdoctoral Science Foundation of Heilongjiang Province(LBH-Z22240)the Heilongjiang University Excellent Youth Foundation。
文摘NiMo-based catalysts show significant potential for the hydrogen evolution reaction(HER).Optimizing the electronic structure and enhancing mass transfer are two critical factors for improving catalytic performance,but they remain significant challenges.Herein,we present a route for synthesizing two-dimensional(2D)porous Mo_(2)N-Ni heterojunction nanosheets with tuned Ni-Mo ratio for enhanced alkaline HER performance.A precursor can be easily synthesized by assembling polyoxometalate clusters(PMo_(12))with layered hydroxy oxides(Ni(OH)_(2)).It is found that the interaction between PMo_(12)and Ni(OH)_(2)can effectively protect the particles from significant agglomeration during pyrolysis,resulting in the formation of 2D porous sheets composed of small Mo_(2)N-Ni units.The transfer of electrons from Ni to Mo_(2)N results in the redistribution of electrons at the heterojunction,optimizing the adsorption and desorption of intermediates.Moreover,the 2D porous structure comprised of small particles enhances mass transfer,thereby reducing the impedance of the catalyst.Consequently,the catalyst with an optimized Mo/Ni ratio exhibits an overpotential of 19 mV at 10 mA cm^(-2),being comparable to that of commercial Pt/C catalyst.The anion exchange membrane(AEM)electrolyzer,consisting of optimized Mo_(2)N-Ni and NiFe-LDH,achieves a current density of 500 mA cm^(-2)at 1.80 V and can operate stably for 300 h.This assembly method offers an effective strategy for the large-scale preparation of efficient catalysts.
基金supported by the National Natural Science Foundation of China(No.12205165)Hebei Province Innovation Ability Improvement Plan Project(No.225676111H).
文摘Structural engineering of Pt-based nanoalloys is crucial for the rational design and manufacturing of high-performance and low-cost electrocatalysts for hydrogen evolution reaction(HER).Here,we reported PtNi nanoparticles with a refined size of 2.71 nm and regular strains loaded on carbon black,synthesized using the high-temperature liquid shock(HTLS)method.This approach offers significant advantages over conventional synthesis methods,including high scalability,rapid reaction rates,and precise control over the size and shape of nanocrystals.Importantly,the synthesized PtNi electrocatalysts demonstrate outstanding catalytic activity and long-term stability for HER,achieving low overpotentials of 19 and 203 mV at current densities of 10 and 1000 mA/cm^(2),respectively.The superior performance can be attributed to the combination of a refined particle size,lattice strains,and synergistic effects between Pt and Ni.This rapid liquid-state synthesis demonstrated here holds great potential for scalable and industrial manufacturing of micro-/nano-catalysts.
基金financial support of the National Natural Science Foundation of China(NSFC)(52394202,52021004,52301232,and 52476056)the Natural Science Foundation of Chongqing Province(2024NSCQ-MSX1109).
文摘The scaling-up of electrochemical CO_(2)reduction requires circumventing the CO_(2)loss as carbonates under alkaline conditions.Zero-gap MEA cell configurations with a proton exchange membrane represent an alternative solution in a pure acidic system,but the catalyst layer in direct contact with the hydrated proton environment usually leads to H_(2)evolution dominating.Herein,we show that polydimethyldiallyl-ammonium-chloride-coated Ag(Ag@PDDA)electrode exhibits outstanding performance with a FE of 86%,a single-pass conversion of 72%,and a stability of 28 h for CO production in pure-acid MEA compared with ammonium poly(N-methyl-piperidine-co-pterphenyl)decorated Ag(Ag/QAPPT)and cetyltrimethylammonium bromide decorated Ag(Ag/CTAB).The in situ ATR-SEIRAS reveal that PDDA creates a positive charge-rich protective outer layer and an N-rich hybrid inner layer,which not only suppresses the migration of H+during the electrolysis process and blocks the direct contact between H2O and Ag catalyst,but also promotes the generation from CO_(2)to*COOH in a pure-acid system.This work highlights the importance of polyelectrolyte engineering in regulating the electrocatalytic interface and accelerates the development of proton exchange membrane CO_(2)electrolysis.
基金support from the National Natural Science Foundation of China(No.22175060).
文摘The hydrogen evolution reaction(HER)is crucial for hydrogen production and sustainable energy storage.Molybdenum disulfide(MoS_(2)),a representative transition metal dichalcogenides(TMDs),shows potential as an HER catalyst but suffers from limited performance due to poor charge transfer and interfacial effects.Here,we report a salt-assisted chemical vapor deposition(CVD)method for synthesizing high-quality tungsten ditelluride(WTe_(2))with tunable morphologies using alkali halides(NaCl,KCl and LiCl).The prepared WTe_(2) nanoribbons and hexagonal nanosheets exhibit morphology-dependent electrical conductivity,with nanosheets showing superior performance.To evaluate WTe_(2) as a contact electrode,WTe_(2)−MoS_(2) heterostructures were fabricated and compared with graphene-MoS_(2) counterparts.The WTe_(2)−MoS_(2) heterostructure exhibits a superior Tafel slope of 111.57 mV/dec and an overpotential of 298 mV at-10 mA/cm^(2),significantly outperforming graphene-based electrodes.This improvement is attributed to the excellent conductivity of WTe_(2) and reduced interfacial Schottky barriers.Moreover,we systematically investigate the influence of WTe_(2) thickness on HER performance and assess the electrochemical durability and structural stability of the heterostructure,further confirming the effectiveness of WTe_(2) as a contact electrode for enhancing the HER activity of MoS_(2).This study offers a novel approach for enhancing the HER performance of MoS_(2) through controlled WTe_(2) growth and application as a contact electrode.Our findings provide valuable insights into the synthesis of high-quality WTe_(2) and broaden the potential applications of two-dimensional materials in energy catalysis.
基金supported by the National Key Research and Development Program of China(2022YFB3805600,2022YFB3805604)the National Natural Science Foundation of China(52201286)+3 种基金the National 111 Project(B20002)the Key R&D Program of Shandong Province,China(2023CXGC010314)the Hubei Provincial Natural Science Foundation of China(2024AFB195)the Fundamental Research Funds for the Central Universities(104972025KFYzxk0014,104972024KFYjlb0008)。
文摘The rationally designed ruthenium selenide(RuSe_(1.6)-500)nanocomposite with selenium vacancies was synthesized via a hydrothermal/annealing approach.During the annealing step,calcination under a H_(2)/Ar atmosphere facilitated the evaporation of selenium,thereby generating selenium vacancies.This study confirmed that RuSe_(1.6)-500 prepared by this method functions as an efficient electrocatalyst for the hydrogen evolution reaction(HER)in seawater.Furthermore,experiments and density functional theory calculations demonstrated that the enhanced electrocatalytic performance and resistance to Cl-induced corrosion in seawater can be attributed to the surface reconstruction of RuSe_(1.6)-500 during the HER process.Specifically,the reconstruction involves the adsorption of hydroxyl groups at selenium vacancies,leading to the formation of a hydroxy-rich surface on RuSe_(1.6)-500.The hydroxy-rich surface is responsible for the superior electrocatalytic activity and stability of RuSe_(1.6)-500 as an electrocatalyst for the HER in seawater.
基金supported by the Development Project of Youth Innovation Team in Shandong Colleges and Universities(No.2019KJC031)the Natural Science Foundation of Shandong Province(Nos.ZR2019MB064,ZR2021MB122 and ZR2022MB137)the Doctoral Program of Liaocheng University(No.318051608).
文摘Pt-based materials are the benchmarked catalysts in the cathodic hydrogen evolution reaction(HER)of water splitting;the prohibitive cost and scarcity of Pt immensely impede the commercialization of hydrogen energy.Ru has aroused significant concern because of its Pt-like activity and much lower price.However,it’s still a top priority to minimize the Ru loading and pursue the most superior cost performance.
基金financially supported by the National Natural Science Foundation of China(No.5217042069)the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(CAST)(No.YESS20200103)the Fundamental Research Funds for the Central Universities(No.265QZ2022004)。
文摘Pt-based nanocatalysts offer excellent prospects for various industries.However,the low loading of Pt with excellent performance for efficient and stable nanocatalysts still presents a considerable challenge.In this study,nanocatalysts with ultralow Pt content,excellent performance,and carbon black as support were prepared through in-situ synthesis.These~2-nm particles uniformly and stably dispersed on carbon black because of the strong s-p-d orbital hybridizations between carbon black and Pt,which suppressed the agglomeration of Pt ions.This unique structure is beneficial for the hydrogen evolution reaction.The catalysts exhibited remarkable catalytic activity for hydrogen evolution reaction,exhibiting a potential of 100 mV at 100 mA·cm^(-2),which is comparable to those of commercial Pt/C catalysts.Mass activity(1.61 A/mg)was four times that of a commercial Pt/C catalyst(0.37 A/mg).The ultralow Pt loading(6.84wt%)paves the way for the development of next-generation electrocatalysts.
基金financially supported by the project of the National Natural Science Foundation of China(52322203)the Key Research and Development Program of Shaanxi Province(2024GHZDXM-21)。
文摘The design of cost-effective and efficient metal-free carbon-based catalysts for the hydrogen evolution reaction(HER)is of great significance for increasing the production of clean hydrogen by the electrolysis of alkaline water.Precise control of the electronic structure by heteroatom doping has proven to be efficient for increasing catalytic activity.Nevertheless,both the structural characteristics and the underlying mechanism are not well understood,especially for doping with two different atoms,thus limiting the use of these catalysts.We report the production of phosphorus and nitrogen co-doped hollow carbon nanospheres(HCNs)by the copolymerization of pyrrole and aniline at a Triton X-100 micelle-interface,followed by doping with phytic acid and carbonization.The unique pore structure and defect-rich framework of the HCNs expose numerous active sites.Crucially,the combined effect of graphitic nitrogen and phosphorus-carbon bonds modulate the local electronic structure of adjacent C atoms and facilitates electron transfer.As a res-ult,the HCN carbonized at 1100°C exhibited superior HER activity and an outstanding stability(70 h at a current density of 10 mA cm^(−2))in alkaline water,because of the large number of graphitic nitrogen and phosphorus-carbon bonds.
基金financial support by the National Natural Science Foundation of China(No.52102241)Doctor of Suzhou University Scientific Research Foundation(Nos.2022BSK019,2020BS015)+2 种基金the Primary Research and Development Program of Anhui Province(No.201904a05020087)the Natural Science Research Project in Universities of Anhui Province in China(Nos.2022AH051386,KJ2021A1114)the Foundation(No.GZKF202211)of State Key Laboratory of Biobased Material and Green Papermaking Qilu University of Technology。
文摘Available online Alkaline water electrolysis(AWE)is a prominent technique for obtaining a sustainable hydrogen source and effectively managing the energy infrastructure.Noble metal-based electrocatalysts,owing to their exceptional hydrogen binding energy,exhibit remarkable catalytic activity and long-term stability in the hydrogen evolution reaction(HER).However,the restricted accessibility and exorbitant cost of noble-metal materials pose obstacles to their extensive adoption in industrial contexts.This review investigates strategies aimed at reducing the dependence on noble-metal electrocatalysts and developing a cost-effective alkaline HER catalyst,while considering the principles of sustainable development.The initial discussion covers the fundamental principle of HER,followed by an overview of prevalent techniques for synthesizing catalysts based on noble metals,along with a thorough examination of recent advancements.The subsequent discussion focuses on the strategies employed to improve noble metalbased catalysts,including enhancing the intrinsic activity at active sites and increasing the quantity of active sites.Ultimately,this investigation concludes by examining the present state and future direction of research in the field of electrocatalysis for the HER.
文摘Photocatalysis provides a promising solution to the worldwide shortages of energy and industrially important raw materials by utilizing sunlight for coupled hydrogen(H_(2))production with controllable organic transformation.Herein,we demonstrate that PtFeNiCoCu high-entropy alloy(HEA)nanocrystals can act as efficient cocatalysts for H_(2)evolution coupled with selective oxidation of cinnamyl alcohol to cinnamaldehyde by cubic cadmium sulfide(CdS)quantum dots(QDs)with uniform sizes of 4.0±0.5 nm.HEA nanocrystals were prepared via a simple solvothermal approach,and were successfully integrated with CdS QDs by an electrostatic self-assembly method to construct HEA/CdS composites.The optimized HEA/CdS sample presented an enhanced photocatalytic H_(2)production rate of 7.15 mmol g^(-1)h^(-1),which was 13 times that of pure CdS QDs.Moreover,a cinnamyl alcohol conversion of 96.2%with cinnamaldehyde selectivity of 99.5%was achieved after photoreaction for 3 h.The integration of HEA with CdS QDs extended the optical absorption edge from 475 to 484 nm.From d-band center analysis,Pt atoms in the HEA are the active sites for H_(2)evolution,exhibiting higher catalytic activity than pure Pt.Meanwhile,the band structure of the CdS QDs enables the oxidative transformation of cinnamyl alcohol to cinnamaldehyde with high selectivity.Moreover,femtosecond transient absorption spectroscopy shows that HEA can significantly promote the separation of photogenerated carriers in CdS,which is vital for achieving enhanced photocatalytic activity.This work inspires atomic-level design of photocatalytic materials for coordinated production of green energy carriers and value-added products.
基金the National Key Research and Development Program of China(No.2022YFB4102000)the National Natural Science Foundation of China(NSFC,Nos.22102018 and 52171201)+4 种基金the Huzhou Science and Technology Bureau(No.2022GZ45)the Hefei National Research Center for Physical Sciences at the Microscale(No.KF2021005)the China Postdoctoral Science Foundation-Funded Project(No.2022M710601)the Huzhou Science and Technology Bureau(No.2023GZ02)the Natural Science Foundation of Sichuan Province(No.24NSFSC5779)。
文摘As hydrogen energy technologies gain momentum,the role of renewable energy in facilitating sustainable hydrogen production is becoming increasingly critical.As a hydrogen production method,water electrolysis has attracted much attention from researchers due to its operational simplicity,the high purity of the hydrogen generated,and its potential for achieving zero carbon emissions throughout the process.Numerous studies has been manipulated on platinum(Pt)-based catalysts,which exhibit superior performance in hydrogen evolution reactions.Within this category,Pt nanoclusters stand out due to their unique attributes,such as quantum size effects and unique coordination environments.These features enable them to outperform both Pt metal atoms and nanoparticles in hydrogen evolution reactions regarding activity and stability.Here,we primarily delve into the reaction mechanisms underlying Pt nanocluster-based hydrogen catalysts,with particular emphasis on the interactions between the metal catalysts and their associated support materials.We provide an exhaustive summary of the strategies employed in the synthesis,the structural analyses conducted,and the performance metrics observed for Pt nanocluster catalysts when paired with various supporting materials.In closing,we explore the future potential and challenges facing Pt nanocluster-based catalysts in the context of industrial water electrolysis,along with emerging avenues for their design and optimization.
基金supported by Research Grants of the NRF(2023R1A2C2003823,RS-2024-00405818)funded by the National Research Foundation under the Ministry of Science,ICT&Future,Korea。
文摘Employing multiple metals for synergistic electronic structure regulation emerges as a promising approach to develop highly efficient and robust electrocatalysts for hydrogen evolution at ampere levels.In this study,a series of Schreibersite-type intermetallic compounds,particularly Mo_(2)Fe_(0.8)Ru_(0.2)P,are synthesized through high-temperature solid-phase synthesis.Experimental results demonstrate that the integration of Ru significantly improves the kinetics of proton adsorption and desorption during the hydrogen evolution reaction(HER).Additionally,density functional theory(DFT)calculations and X-ray absorption near edge structure(XANES)analyses effectively corroborate the pronounced d-orbital hybridization of Fe within the structure,which facilitates the transfer of hydroxide ions and the maintenance of material durability during alkaline HER processes.Remarkably,Mo_(2)Fe_(0.8)Ru_(0.2)P exhibits superior alkaline HER activity,characterized by an overpotential of merely 48 mV at a current density of 10 mA cm^(-2).After prolonged operation of 1000 h at high current densities(1.1 A cm^(-2)),the activity decline remains minimal,under 4%(with overpotential increasing from 258 mV to 268 mV).These results demonstrate the potential of strategically combining metallic elements to design high-performance industrial-grade electrocatalysts.
基金the German Research Foundation (DFG) under Germany's excellence strategy–EXC 2089/1–390776260, Germany's excellence cluster “e-conversion”the DFG project BA 5795/6-1+2 种基金funding from the European Union's Horizon 2020 research and innovation program under grant agreement HERMES No 952184the National Science Foundation (NSF) support through the NSF CAREER award (Grant No. CBET1941204)financial support from TUM Innovation Network for Artificial Intelligence powered Multifunctional Material Design (ARTEMIS).
文摘The effects of seemingly inert alkali metal(AM)cations on the electrocatalytic activity of electrode materials towards reactions essential for energy provision have become the emphasis of substantial research efforts in recent years.The hydrogen and oxygen evolution reactions during alkaline water electrolysis and the oxygen electro-reduction taking place in fuel cells are of particular importance.There is no universal theory explaining all the details of the AM cation effect in electrocatalysis.For example,it remains unclear how“spectator”AM-cations can change the kinetics of electrocatalytic reactions often more significantly than the modifications of the elec-trode structure and composition.This situation originates partly from a lack of systematic experimental and theoretical studies of this phenomenon.The present work exploits impedance spectroscopy to investigate the influence of the AM cations on the mechanism of the hydrogen evolution reaction at Pt microelectrodes.The activity follows the trend:Li^(+)≥Na^(+)≥K^(+)≥Cs^(+),where the highest activity corresponds to 0.1 M LiOH electrolytes at low overpotentials.We demonstrate that the nature of the AM cations also changes the relative contribution of the Volmer–Heyrovsky and Volmer–Tafel mechanisms to the overall reaction,with the former being more important for LiOH electrolytes.Our density functional theory-based thermodynamics and molecular dynamics calculations support these findings.
基金supported by the National Natural Science Foundation of China(No.52102470)。
文摘As a clean energy source,hydrogen plays a critical role in the global mission to achieve carbon neutrality.Among varied hydrogen production techniques,water electrolysis driven by clean energy,such as solar or wind energy,is the most promising and viable option,with the advantages of celerity,high efficiency,cleanliness,and sustainability.However,this process necessitates a highly active and durable hydrogen evolution reaction(HER)catalyst to enhance the overall reaction efficiency.This article thoroughly reviews the recent development of electrocatalysts exhibiting high-performance HER.In particular,a comprehensive look at noble metals platinum(Pt),ruthenium(Ru),iridium(Ir),and non-noble metals,including sulfides,carbides,nitrides and phosphides is taken.Synthesis strategies,methods for enhancing performance,and the correlation between structure,composition,and catalytic performance are discussed.We also pay particular attention to density functional theory(DFT)calculations to reveal the mechanisms behind the improvement of HER performance.Finally,the critical challenges associated with electrochemical water splitting and propose coping strategies are presented.
基金the final support of ARC DP220103045the startup support of KFUPMPrince Sultan University for their support。
文摘Transition metal carbides,known as MXenes,particularly Ti_(3)C_(2)T_(x),have been extensively explored as promising materials for electrochemical reactions.However,transition metal carbonitride MXenes with high nitrogen content for electrochemical reactions are rarely reported.In this work,transition metal carbonitride MXenes incorporated with Pt-based electrocatalysts,ranging from single atoms to sub-nanometer dimensions,are explored for hydrogen evolution reaction(HER).The fabricated Pt clusters/MXene catalyst exhibits superior HER performance compared to the single-atom-incorporated MXene and commercial Pt/C catalyst in both acidic and alkaline electrolytes.The optimized sample shows low overpotentials of 28,65,and 154 mV at a current densities of 10,100,and 500 m A cm^(-2),a small Tafel slope of 29 m V dec^(-1),a high mass activity of 1203 mA mgPt^(-1)and an excellent turnover frequency of 6.1 s^(-1)in the acidic electrolyte.Density functional theory calculations indicate that this high performance can be attributed to the enhanced active sites,increased surface functional groups,faster charge transfer dynamics,and stronger electronic interaction between Pt and MXene,resulting in optimized hydrogen absorption/desorption toward better HER.This work demonstrates that MXenes with a high content of nitrogen may be promising candidates for various catalytic reactions by incorporating single atoms or clusters.
文摘The issues of fossil energy shortage and environmental pollution caused by the excessive consumption of conventional fossil fuels necessitates the exploration of renewable and clean energy sources such as hydrogen,which is viable alternative to traditional energy sources in view of its high energy density and nonpolluting nature.In this regard,photocatalytic technology powered by inexhaustible solar energy is an ideal hydrogen production method.The recently developed copper-and zinc-based multinary metal sulfide(MMS)semiconductor photocatalysts exhibit the advantages of suitable bandgap,wide light-harvesting range,and flexible elemental composition,thus possessing great potential for achieving considerable photocatalytic hydrogen evolution(PHE)performance.Despite great progress has been achieved,the current photocatalysts still cannot meet the commercial application demands,which highlights the mechanisms understanding and optimization strategies for efficient PHE.Herein,the basic mechanisms of PHE,and effective optimization strategies are firstly introduced.Afterwards,the research process and the performance of copper-and zinc-based MMS photocatalysts,are thoroughly reviewed.Finally,the unresolved issues,and challenges hindering the achievement of overall water splitting have been discussed.
基金supported by the Young Project of the Education Department in Guizhou Province(No.2022099)the Natural Science Special of Guizhou University(No.X202220 Special Post A).
文摘Ru-based nanomaterials have been demonstrated to be highly active electrocatalysts for hydrogen evo-lution reaction(HER),yet weak water adsorption and splitting ability in neutral media thus it is rather difficult for the intermediates to adsorb on the active site.Herein,we introduce a concept of the prox-imity effect,com prising adjacent Ru and RuO_(2) nanoparticles coupled on TiO_(2)(Ru/RuO_(2)-TiO_(2)),for the synergic promotion of water molecule adsorption and splitting,significantly enhancing HER electrocatal-ysis performance.The in-situ spectroscopy experiments and density function theory(DFT)simulations demonstrated that the proximity effect between the adjacent Ru nanoparticles and RuO_(2) nanoparticles can accelerate water adsorption and splitting.As a result,the as-made Ru/RuO_(2)-TiO_(2) only need overpo-tentials of 52.7,16.0,and 16.4 mV to achieve the current density of 10 mA cm-2 in neutral,acid,and alkaline media,respectively.The mass activity of Ru/RuO_(2)-TiO_(2) in neutral media is 320 and 117 times higher than that of commercial Ru/C and Pt/C at the overpotential of 100 mV,respectively.This work emphasizes the proximity effect for activation of reactants which can be extended to other electrocat-alytic reactions.
基金supported by National Natural Science Foundation of China(NSFC,22338006,92356301,9235630033 and 22375062)Shanghai Municipal Science and Technology Major Project(21JC1401700)+4 种基金Shanghai Pilot Program for Basic Research(22TQ1400100-10)Fundamental Research Funds for the Central UniversitiesShanghai Pujiang Program(22PJ1402400)“Chenguang Program”supported by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(22CGA32)the Young Elite Scientists Sponsorship Program by CAST(2023QNRC001).
文摘Organic nanophotocatalysts are promising candidates for solar fuels production,but they still face the challenge of unfavorable geminate recombination due to the limited exciton diffusion lengths.Here,we introduce a binary nanophotocatalyst fabricated by blending two polymers,PS-PEG5(PS)and PBT-PEG5(PBT),with matched absorption and emission spectra,enabling a Forster resonance energy transfer(FRET)process for enhanced photocatalysis.These heterostructure nanophotocatalysts are processed using a facile and scalable flash nanoprecipitation(FNP)technique with precious kinetic control over binary nanoparticle formation.The resulting nanoparticles exhibit an exceptional photocatalytic hydrogen evolution rate up to 65 mmol g^(-1) h^(-1),2.5 times higher than that single component nanoparticles.Characterizations through fluorescence spectra and transient absorption spectra confirm the hetero-energy transfer within the binary nanoparticles,which prolongs the excited-state lifetime and extends the namely“effective exciton diffusion length”.Our finding opens new avenues for designing efficient organic photocatalysts by improving exciton migration.
