质子交换膜水电解槽(PEMWE)因其在低温下的高效率和高功率密度,成为新一代电解槽的发展方向.在水的电解过程中,设计高效稳定的析氢反应(HER)和析氧反应(OER)催化剂是进一步提高电解槽应用的前提.根据HER和OER“火山型”分布曲线,贵金属(...质子交换膜水电解槽(PEMWE)因其在低温下的高效率和高功率密度,成为新一代电解槽的发展方向.在水的电解过程中,设计高效稳定的析氢反应(HER)和析氧反应(OER)催化剂是进一步提高电解槽应用的前提.根据HER和OER“火山型”分布曲线,贵金属(Ir,Ru等)依然是主要的基准电催化剂.对于酸性条件下全水分解,Ir基和Ru基双功能催化剂仍然是最常见的选择.然而,与Ir基催化剂相比,Ru基催化剂在酸性条件下的高溶解速率易导致催化剂快速失活,大大降低了其实际应用价值.目前,酸性条件下全水分解的Ir基催化剂也取得了一些成果,如合金(如PdCu/Ir,Au@AuIr_(2),IrTe纳米棒和IrNi合金纳米花)、钙钛矿(如AIrO_(3))、硒化物(如Li-IrSe_(2))和团簇(如Ir纳米团簇,IrNi纳米团簇)等.然而,Ir基材料在高电流密度下仍然面临质量活性低和稳定性有限的挑战(100 mA cm^(-2)时的过电位超过420 mV,酸性整体水分解在高电流密度下的长期稳定性差).上述问题使得电催化剂无法满足PEMWE的应用要求.因此,开发具有优异电化学活性和稳定性的新型Ir基电催化剂成为当务之急.近年来,至少由五种元素组成的高熵合金(HEAs)材料具有在极端条件下的硬度、韧性、腐蚀性和热稳定性等的强耐受性,因而引起了研究者的广泛兴趣.同时,不同组分的可控性也赋予了HEAs固有的晶格畸变和可调电子结构的协同效应,在催化领域也发挥着重要作用.目前,尚未见使用HEAs催化剂进行酸性条件下全水分解的相关报道.从形貌上看,金属烯具有表面金属原子体积比大、表面金属缺陷丰富、稳定性较好等优点,从而表现出较好的催化性能.因此,结合HEAs协同效应和金属烯结构优点的电催化剂,有望解决酸性条件下全水分解电催化剂的设计问题.本文成功制备了具有丰富的无定形和晶体结构的IrPdRhMoW HEA金属烯作为一种高效的双功能电催化剂,用于酸性条件下全水分解.在0.5 mol L^(-1)H_(2)SO_(4)溶液中,IrPdRhMoW/C在10 mA cm^(-2)下HER和OER的过电位分别为15和188 mV,远强于商业催化剂(HER:Pt/C,47 mV和OER:RuO_(2),305 mV)和大部分已报道的贵金属基催化剂.使用IrPdRhMoW/C进行全水分解,只需1.48 V的电池电压即可获得10 mA cm^(-2)的电流密度,而实现100 mA cm^(-2)的电流密度所需的电池电压为1.59 V.IrPdRhMoW/C在100 mA cm^(-2)水分解100 h后仍保持较好的电活性和结构稳定性,这也是在高电流密度下实现酸性条件下全水分解的长期稳定性.密度泛函理论计算结果表明,由于晶体和非晶结构的共存,HEA中电子结构的具有自平衡效应.强轨道耦合不仅最大限度地提高了对HER和OER的电活性,而且稳定了金属位点的价态,以实现持久的电催化全水分解.综上,本工作不仅成功制备了HEA金属烯,而且将其应用于酸性条件下全水分解.此外,电荷自平衡效应可以解决酸性条件下全水分解过程中活性与稳定性之间的问题,且有望进一步应用到其他电催化剂的设计和合成中.展开更多
The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A sel...The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A self-supporting,multiscale porous NiFeZn/NiZn-Ni catalyst with a triple interface heterojunction on nickel foam(NF)(NiFeZn/NiZn-Ni/NF)was in-situ fabricated using an electroplating-annealing-etching strategy.The unique multiinterface engineering and three-dimensional porous scaffold significantly modify the mass transport and electron interaction,resulting in superior bifunctional electrocatalytic performance for water splitting.The NiFeZn/NiZn-Ni/NF catalyst demonstrates low overpotentials of 187 m V for HER and 320 mV for OER at a current density of 600 mA/cm^(2),along with high durability over 150 h in alkaline solution.Furthermore,an electrolytic cell assembled with NiFeZn/NiZn-Ni/NF as both the cathode and anode achieves the current densities of 600 and 1000 m A/cm^(2) at cell voltages of 1.796 and 1.901 V,respectively,maintaining the high stability at 50 mA/cm^(2) for over 100 h.These findings highlight the potential of NiFeZn/NiZn-Ni/NF as a cost-effective and highly efficient bifunctional electrocatalyst for overall water splitting.展开更多
Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation o...Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.展开更多
The exploration of stable and highly efficient alkaline hydrogen evolution reaction(HER)electrocatalysts is imperative for alkaline water splitting.Herein,Se-doped NiCoP with hierarchical nanoarray structures directly...The exploration of stable and highly efficient alkaline hydrogen evolution reaction(HER)electrocatalysts is imperative for alkaline water splitting.Herein,Se-doped NiCoP with hierarchical nanoarray structures directly grown on carbon cloth(Se-NiCoP/CC)was prepared by hydrothermal reaction and phosphorization/selenization process.The experimental results reveal that Se doping could increase the electrochemical active sites and alter the electronic structure of NiCoP.The optimized Se-NiCoP/CC electrode exhibits outstanding HER activity in alkaline electrolyte,which only needs a low overpotential of 79 mV at the current density of 10 mA/cm^(2).When serving as anode and cathode electrode simultaneously,the Se-NiCoP/CC electrodes achieve current density of 50 mA/cm^(2) at a low voltage of only 1.62 V.This work provides a feasible way to rationally design high active HER electrocatalysts.展开更多
In an attempt to develop low-cost,non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media,cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C3N...In an attempt to develop low-cost,non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media,cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C3N4 as the carbon source on a 3D porous nickel foam substrate.Benefiting from the optimized electronic structure and enhanced mass and charge transport,as well as the 3D conducting pathway,MoxCoy@N-CNSs/CNTs shows superior performance towards both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in an alkaline medium.The optimal electrocatalyst is Mo2Co1@N-CNSs/CNTs,which reveals a current density of 10 mA cm^-2 at the low overpotentials of 99 mV and 300 mV for the HER and OER,respectively,and a relatively low cell voltage(1.63 V)for the overall water electrolysis.The method of optimizing the composition and nanostructure of a material provides a new avenue for the development and utilization of high-performance electrocatalysts.展开更多
Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices.Up to now,various types of nanostructured materials have been studied as advanced electrocatalysts.This review highligh...Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices.Up to now,various types of nanostructured materials have been studied as advanced electrocatalysts.This review highlights the application of one‐dimensional(1D)metal electrocatalysts in energy conversion,focusing on two important reaction systems-direct methanol fuel cells and water splitting.In this review,we first give a broad introduction of electrochemical energy conversion.In the second section,we summarize the recent significant advances in the area of 1D metal nanostructured electrocatalysts for the electrochemical reactions involved in fuel cells and water splitting systems,including the oxygen reduction reaction,methanol oxidation reaction,hydrogen evolution reaction,and oxygen evolution reaction.Finally,based on the current studies on 1D nanostructures for energy electrocatalysis,we present a brief outlook on the research trend in 1D nanoelectrocatalysts for the two clean electrochemical energy conversion systems mentioned above.展开更多
Efficient,stable,and noble‐metal‐free electrocatalysts for both the oxygen evolution reaction and the hydrogen evolution reaction are highly imperative for the realization of low‐cost commercial water‐splitting el...Efficient,stable,and noble‐metal‐free electrocatalysts for both the oxygen evolution reaction and the hydrogen evolution reaction are highly imperative for the realization of low‐cost commercial water‐splitting electrolyzers.Herein,a cost‐effective and ecofriendly strategy is reported to fabricate coral‐like FeNi(OH)x/Ni as a bifunctional electrocatalyst for overall water splitting in alkaline media.With the assistance of mild corrosion of Ni by Fe(NO3)3,in situ generated FeNi(OH)x nanosheets are intimately attached on metallic coral‐like Ni.Integration of these nanosheets with the electrodeposited coral‐like Ni skeleton and the supermacroporous Ni foam substrate forms a binder‐free hierarchical electrode,which is beneficial for exposing catalytic active sites,accelerating mass transport,and facilitating the release of gaseous species.In 1.0 mol L^-1 KOH solution,a symmetric electrolyzer constructed with FeNi(OH)x/Ni as both the anode and the cathode exhibits an excellent activity with an applied potential difference of 1.52 V at 10 mA cm^-2,which is superior to that of an asymmetric electrolyzer constructed with the state‐of‐the‐art RuO2‐PtC couple(applied potential difference of 1.55 V at 10 mA cm^-2).This work contributes a facile and reliable strategy for manufacturing affordable,practical,and promising water‐splitting devices.展开更多
The generation of hydrogen through the electrolysis of water has attracted attention as a promising way to produce and store energy using renewable energy sources.In this process,a catalyst is very important to achiev...The generation of hydrogen through the electrolysis of water has attracted attention as a promising way to produce and store energy using renewable energy sources.In this process,a catalyst is very important to achieve a high‐energy conversion efficiency for the electrolysis of water.A good catalyst for water electrolysis should exhibit high catalytic activity,good stability,low cost and good scalability.Much research has been devoted to developing efficient catalysts for both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Traditionally,it has been accepted that a material with high crystallinity is important to serve as a good catalyst for HER and/or OER.Recently,catalysts for HER and/or OER in the electrolysis of water splitting based on amorphous materials have received much interest in the scientific community owing to the abundant unsaturated active sites on the amorphous surface,which form catalytic centers for the reaction of the electrolysis of water.We summarize the recent advances of amorphous catalysts for HER,OER and overall water splitting by electrolysis and the related fundamental chemical reactions involved in the electrolysis of water.The current challenges confronting the electrolysis of water and the development of more efficient amorphous catalysts are also discussed.展开更多
Two-dimensional(2D)carbon nitride(CN)photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties.In this study,we successfully prepared CN materials with heterogeneous structur...Two-dimensional(2D)carbon nitride(CN)photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties.In this study,we successfully prepared CN materials with heterogeneous structures via hydrothermal treatment,high-temperature roasting,ball milling,sintering,and other processes.Benefitting from interface interactions in hybrid architectures,the CN photocatalysts exhibited high photocatalytic activity.The rate of hydrogen production using these CN photocatalysts reached 17028.82μmol h^(−1)g^(−1),and the apparent quantum efficiency was 11.2%at 420 nm.The ns-level time-resolved photoluminescence(PL)spectra provided information about the time-averaged lifetime of fluorescence charge carriers;the lifetime of the charge carriers causing the fluorescence of CN reached 9.99 ns.Significantly,the CN photocatalysts displayed satisfactory results in overall water splitting without the addition of sacrificial agents.The average hydrogen and oxygen production rates were 270.95μmol h^(−1)g^(−1)and 115.21μmol h^(−1)g^(−1)in 7 h,respectively,which were promising results for the applications of the catalysts in overall water splitting processes.We investigated the high efficiency of the prepared CN photocatalysts via a series of tests(UV-vis diffuse reflectance spectroscopy,photocurrent response measurements,PL emission spectroscopy,time-resolved PL spectroscopy,and Brunauer-Emmett-Teller analysis).Furthermore,the Mott-Schottky plot and current-voltage curve were acquired via electrochemical tests.The fabricated CN photocatalyst had a small p-n junction in its heterogeneous structure,which further enhanced its photocatalytic efficiency.Therefore,this work can promote the development of CN photocatalysts.展开更多
Step-scheme(S-scheme)heterojunctions in photocatalysts can provide novel and practical insight on promoting photogenerated carrier separation.The latter is critical in controlling the overall efficiency in one-step ph...Step-scheme(S-scheme)heterojunctions in photocatalysts can provide novel and practical insight on promoting photogenerated carrier separation.The latter is critical in controlling the overall efficiency in one-step photoexcitation systems.In this study,a nanosized BiVO4/Bi0.6Y0.4VO4 solid solution was prepared by a coprecipitation method following with hydrothermal or calcination processes.The S-scheme heterojunction was fabricated by in-situ pressure-induced transformations of bismuth vanadate from the tetragonal zircon phase to the monoclinic scheelite phase,which led to the formation of BiVO4 nanoparticles with a diameter of approximately 5 nm on the surface of BiVO_(4)/Bi_(0.6)Y_(0.4)VO_(4)/Bi_(0.6)Y_(0.4)VO_(4) with S-scheme heterojunctions showed significantly enhanced photocatalytic overall water splitting activity compared with using bare BiVO_(4)/Bi_(0.6)Y_(0.4)VO_(4).Characterization of the carrier dynamics demonstrated that a superior carrier separation through S-type heterojunctions might have caused the enhanced overall water splitting(OWS)activity.Surface photovoltage spectra and the results of selective photodeposition experiments indicated that the photogenerated holes mainly migrated to the BiVO4 nanoparticles in the heterojunction.This confirmed that the charge transfer route corresponds to an S-scheme rather than a type-II heterojunction mechanism under light illumination.This study presents a facile and efficient strategy to construct S-scheme heterojunctions through a pressure-induced phase transition.The results demonstrated that S-scheme junctions composed of different crystalline phases can boost the carrier separation capacity and eventually improve the photocatalytic OWS activity.展开更多
Designing low-cost, highly efficient, and stable bifunctional electrocatalysts for both hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is of vital significance for water splitting.Herein, thre...Designing low-cost, highly efficient, and stable bifunctional electrocatalysts for both hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is of vital significance for water splitting.Herein, three-dimensional lily-like CoNi_2S_4 supported on nickel foam(CoNi_2S_4/Ni) has been fabricated by sulfuration of the Co–Ni precursor. As expected, CoNi_2S_4/Ni possesses such outstanding electrocatalytic properties that it requires an overpotential of only 54 mV at 10 mA cm^(-2) and 328 mV at 100 mA cm^(-2) for HER and OER, respectively. Furthermore, by utilizing the CoNi_2S_4/Ni electrodes as bifunctional electrocatalysts for overall water splitting, a current density of 10 mA cm^(-2) can be obtained at a voltage of only 1.56 V.展开更多
When a proton reduction cocatalyst is loaded on an n-type semiconductor for photocatalytic overall water splitting(POWS),the location of water oxidation sites is generally considered at the surface of the semiconducto...When a proton reduction cocatalyst is loaded on an n-type semiconductor for photocatalytic overall water splitting(POWS),the location of water oxidation sites is generally considered at the surface of the semiconductor due to upward band-bending of n-type semiconductor which may ease the transfer of the photogenerated holes to the surface.However,this is not the case for Pt/SrTiO_(3),a model semiconductor based photocatalyst for POWS.It was found that the photogenerated holes are more readily accumulated at the interface between Pt cocatalyst and SrTiO_(3) photocatalyst as probed by photo-oxidative deposition of PbO_(2),indicating that the water oxidation sites are located at the interface between Pt and SrTiO_(3).Electron paramagnetic resonance and scanning transmission electron microscope studies suggest that the interfacial oxygen atoms between Pt and SrTiO_(3) in Pt/SrTiO_(3) after POWS are more readily lost to form oxygen vacancies upon vacuum heat treatment,regardless of Pt loading by photodeposition or impregnation methods,which may serve as additional support for the location of the active sites for water oxidation at the interface.Density functional theory calculations also suggest that the oxygen evolution reaction more readily occurs at the interfacial sites with the lowest overpotential.These experimental and theoretical studies reveal that the more active sites for water oxidation are located at the interface between Pt and SrTiO_(3),rather than on the surface of SrTiO_(3).Hence,the tailor design and control of the interfacial properties are extremely important for the achievement or improvement of the POWS on cocatalyst loaded semiconductor photocatalyst.展开更多
Efficient and stable bifunctional electrocatalysts for water splitting is essential for producing hydrogen and alleviating huge energy consumption.Meanwhile,charge transfer engineering is an efficient approach to modu...Efficient and stable bifunctional electrocatalysts for water splitting is essential for producing hydrogen and alleviating huge energy consumption.Meanwhile,charge transfer engineering is an efficient approach to modulate the localized electronic properties of catalysts and tune the electrocatalytic performance.Herein,we tactfully fabricate PtFeNi alloys/NiFe layered double hydroxides(LDHs)heterostructure by an easily electrochemical way with a small amount of Pt.The experimental and theoretical results unravel that the charge transfer on the alloy clusters modulated by the defective substrates(NiFe LDHs),which synergistically optimizes the adsorption energy of the reaction intermediates.The electrocatalyst exhibits an ultra‐low overpotential of 81 and 243 mV at the current density of 100 mA cm^(–2) for hydrogen evolution and oxygen evolution,respectively.Furthermore,the overall water splitting indicates that PtFeNi alloys/NiFe LDHs presents an ultra‐low overpotential of 265 and 406 mV to reach the current density of 10 and 300 mA cm^(–2),respectively.It proves that the PtFeNi alloys/NiFe LDHs catalyst is an excellent dual‐function electrocatalyst for water splitting and promising for industrialization.This work provides a new electrochemical approach to construct the alloy heterostructure.The prepared heterostructures act as an ideal platform to investigate the charge re‐distribution behavior and to improve the electrocatalytic activity.展开更多
Investigation of the charge dynamics and roles of cocatalysts is crucial for understanding the reaction of photocatalytic water splitting on semiconductor photocatalysts.In this work,the dynamics of photogenerated ele...Investigation of the charge dynamics and roles of cocatalysts is crucial for understanding the reaction of photocatalytic water splitting on semiconductor photocatalysts.In this work,the dynamics of photogenerated electrons in Ga_(2)O_(3) loaded with Cr_(2)O_(3)-Rh cocatalysts was studied using time-resolved mid-infrared spectroscopy.The structure of these Cr_(2)O_(3)-Rh cocatalysts was identified with high-resolution transmission electron microscopy and CO adsorption Fourier-transform infrared spectroscopy,as Rh particles partly covered with Cr_(2)O_(3).The decay dynamics of photogenerated electrons reveals that only the electrons trapped by the Rh particles efficiently participate in the H2 evolution reaction.The loaded Cr_(2)O_(3) promotes electron transfer from Ga_(2)O_(3) to Rh,which accelerates the electron-consuming reaction for H2 evolution.Based on these observations,a photocatalytic water-splitting mechanism for Cr_(2)O_(3)-Rh/Ga_(2)O_(3) photocatalysts has been proposed.The elucidation of the roles of the Cr_(2)O_(3)-Rh cocatalysts aids in further understanding the reaction mechanisms of photocatalytic water splitting and guiding the development of improved photocatalysts.展开更多
Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synt...Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.展开更多
The paper presents the research for the purpose of selecting microorganisms into the production process of "chao" to improve the quality of "chao" products and ensure food safety. Several analytical methods such a...The paper presents the research for the purpose of selecting microorganisms into the production process of "chao" to improve the quality of "chao" products and ensure food safety. Several analytical methods such as determination of formal nitrogen, determination of the protease hydrolysis activity, sensory evaluation method, experimental procedure, methods of analysis and processing of empirical data were used in this study. The findings showed that two out of four selected microorganism strains (one strain of fungi and three strains of bacteria denoted NM1, VK1, VK2, VK3, respectively) were the most appropriate for the cooperation among them and the production of %hao", which were coded NM1 and VK1. The suitable mixing proportion of strains of NM1 and VK1 was determined at 1:1.25, compatible with the 1:100 ratio of the varieties of microorganisms (in powder form) to tofu.展开更多
Based on the upper bound theorem of limit analysis,the factor of safety for shallow tunnel in saturated soil is calculated in conjunction with the strength reduction technique.To analyze the influence of the pore pres...Based on the upper bound theorem of limit analysis,the factor of safety for shallow tunnel in saturated soil is calculated in conjunction with the strength reduction technique.To analyze the influence of the pore pressure on the factor of safety for shallow tunnel,the power of pore pressure is regarded as a power of external force in the energy calculation.Using the rigid multiple-block failure mechanism,the objective function for the factor of safety is constructed and the optimal solutions are derived by employing the sequential quadratic programming.According to the results of optimization calculation,the factor of safety of shallow tunnel for different pore pressure coefficients and variational groundwater tables are obtained.The parameter analysis shows that the pore pressure coefficient and the location of the groundwater table have significant influence on the factor of safety for shallow tunnel.展开更多
文摘质子交换膜水电解槽(PEMWE)因其在低温下的高效率和高功率密度,成为新一代电解槽的发展方向.在水的电解过程中,设计高效稳定的析氢反应(HER)和析氧反应(OER)催化剂是进一步提高电解槽应用的前提.根据HER和OER“火山型”分布曲线,贵金属(Ir,Ru等)依然是主要的基准电催化剂.对于酸性条件下全水分解,Ir基和Ru基双功能催化剂仍然是最常见的选择.然而,与Ir基催化剂相比,Ru基催化剂在酸性条件下的高溶解速率易导致催化剂快速失活,大大降低了其实际应用价值.目前,酸性条件下全水分解的Ir基催化剂也取得了一些成果,如合金(如PdCu/Ir,Au@AuIr_(2),IrTe纳米棒和IrNi合金纳米花)、钙钛矿(如AIrO_(3))、硒化物(如Li-IrSe_(2))和团簇(如Ir纳米团簇,IrNi纳米团簇)等.然而,Ir基材料在高电流密度下仍然面临质量活性低和稳定性有限的挑战(100 mA cm^(-2)时的过电位超过420 mV,酸性整体水分解在高电流密度下的长期稳定性差).上述问题使得电催化剂无法满足PEMWE的应用要求.因此,开发具有优异电化学活性和稳定性的新型Ir基电催化剂成为当务之急.近年来,至少由五种元素组成的高熵合金(HEAs)材料具有在极端条件下的硬度、韧性、腐蚀性和热稳定性等的强耐受性,因而引起了研究者的广泛兴趣.同时,不同组分的可控性也赋予了HEAs固有的晶格畸变和可调电子结构的协同效应,在催化领域也发挥着重要作用.目前,尚未见使用HEAs催化剂进行酸性条件下全水分解的相关报道.从形貌上看,金属烯具有表面金属原子体积比大、表面金属缺陷丰富、稳定性较好等优点,从而表现出较好的催化性能.因此,结合HEAs协同效应和金属烯结构优点的电催化剂,有望解决酸性条件下全水分解电催化剂的设计问题.本文成功制备了具有丰富的无定形和晶体结构的IrPdRhMoW HEA金属烯作为一种高效的双功能电催化剂,用于酸性条件下全水分解.在0.5 mol L^(-1)H_(2)SO_(4)溶液中,IrPdRhMoW/C在10 mA cm^(-2)下HER和OER的过电位分别为15和188 mV,远强于商业催化剂(HER:Pt/C,47 mV和OER:RuO_(2),305 mV)和大部分已报道的贵金属基催化剂.使用IrPdRhMoW/C进行全水分解,只需1.48 V的电池电压即可获得10 mA cm^(-2)的电流密度,而实现100 mA cm^(-2)的电流密度所需的电池电压为1.59 V.IrPdRhMoW/C在100 mA cm^(-2)水分解100 h后仍保持较好的电活性和结构稳定性,这也是在高电流密度下实现酸性条件下全水分解的长期稳定性.密度泛函理论计算结果表明,由于晶体和非晶结构的共存,HEA中电子结构的具有自平衡效应.强轨道耦合不仅最大限度地提高了对HER和OER的电活性,而且稳定了金属位点的价态,以实现持久的电催化全水分解.综上,本工作不仅成功制备了HEA金属烯,而且将其应用于酸性条件下全水分解.此外,电荷自平衡效应可以解决酸性条件下全水分解过程中活性与稳定性之间的问题,且有望进一步应用到其他电催化剂的设计和合成中.
基金financially supported from the National Natural Science Foundation of China(No.52201254)the Natural Science Foundation of Shandong Province,China(Nos.ZR2023ME155,ZR2020MB090,ZR2020QE012,ZR2020MB027)+1 种基金the Project of“20 Items of University”of Jinan,China(No.202228046)the Taishan Scholar Project of Shandong Province,China(No.tsqn202306226)。
文摘The development of efficient nonprecious bifunctional electrocatalysts for water electrolysis is crucial to enhance the sluggish kinetics of the oxygen evolution reaction(OER)and hydrogen evolution reaction(HER).A self-supporting,multiscale porous NiFeZn/NiZn-Ni catalyst with a triple interface heterojunction on nickel foam(NF)(NiFeZn/NiZn-Ni/NF)was in-situ fabricated using an electroplating-annealing-etching strategy.The unique multiinterface engineering and three-dimensional porous scaffold significantly modify the mass transport and electron interaction,resulting in superior bifunctional electrocatalytic performance for water splitting.The NiFeZn/NiZn-Ni/NF catalyst demonstrates low overpotentials of 187 m V for HER and 320 mV for OER at a current density of 600 mA/cm^(2),along with high durability over 150 h in alkaline solution.Furthermore,an electrolytic cell assembled with NiFeZn/NiZn-Ni/NF as both the cathode and anode achieves the current densities of 600 and 1000 m A/cm^(2) at cell voltages of 1.796 and 1.901 V,respectively,maintaining the high stability at 50 mA/cm^(2) for over 100 h.These findings highlight the potential of NiFeZn/NiZn-Ni/NF as a cost-effective and highly efficient bifunctional electrocatalyst for overall water splitting.
文摘Perovskite SrTaO_(2)N is one of the most promising narrow-bandgap photocatalysts for Z-scheme overall water splitting.However,the formation of defect states during thermal nitridation severely hinders the separation of charges,resulting in poor photocatalytic activity.In the present study,we successfully synthesize SrTaO_(2)N photocatalyst with low density of defect states,uniform morphology and particle size by flux-assisted one-pot nitridation combined with Mg doping.Some important parameters,such as the size of unit cell,the content of nitrogen,and microstructure,prove the successful doping of Mg.The defect-related carrier recombination has been significantly reduced by Mg doping,which effectively promotes the charge separation.Moreover,Mg doping induces a change of the band edge,which makes proton reduction have a stronger driving force.After modifying with the core/shell-structured Pt/Cr_(2)O_(3)cocatalyst,the H_(2)evolution activity of the optimized SrTaO_(2)N:Mg is 10 times that of the undoped SrTaO_(2)N,with an impressive apparent quantum yield of 1.51%at 420 nm.By coupling with Au-FeCoO_(x)modified BiVO_(4)as an O_(2)-evolution photocatalyst and[Fe(CN)_(6)]_(3)−/[Fe(CN)_(6)]_(4)−as the redox couple,a redox-based Z-scheme overall water splitting system is successfully constructed with an apparent quantum yield of 1.36%at 420 nm.This work provides an alternative way to prepare oxynitride semiconductors with reduced defects to promote the conversion of solar energy.
基金Projects(51772086,51872087,51971089)supported by the National Natural Science Foundation of ChinaProject(2018TP1037-202102)supported by Open Fund of Hunan Provincial Key Laboratory of Advanced Materials for New Energy Storage and Conversion,China+1 种基金Project supported by Student National SIT Innovation Program,ChinaProject(2020CB1007)supported by Hunan Joint International Laboratory of Advanced Materials and Technology for Clean Energy,China。
文摘The exploration of stable and highly efficient alkaline hydrogen evolution reaction(HER)electrocatalysts is imperative for alkaline water splitting.Herein,Se-doped NiCoP with hierarchical nanoarray structures directly grown on carbon cloth(Se-NiCoP/CC)was prepared by hydrothermal reaction and phosphorization/selenization process.The experimental results reveal that Se doping could increase the electrochemical active sites and alter the electronic structure of NiCoP.The optimized Se-NiCoP/CC electrode exhibits outstanding HER activity in alkaline electrolyte,which only needs a low overpotential of 79 mV at the current density of 10 mA/cm^(2).When serving as anode and cathode electrode simultaneously,the Se-NiCoP/CC electrodes achieve current density of 50 mA/cm^(2) at a low voltage of only 1.62 V.This work provides a feasible way to rationally design high active HER electrocatalysts.
基金supported by the National Natural Science Foundation of China(51622102,51571124,21421001)the 111 Project(B12015)+1 种基金the Natural Science Foundation of Tianjin(18ZXJMTG00040,16PTSYJC00030)the Fundamental Research Funds for the Central Universities~~
文摘In an attempt to develop low-cost,non-noble-metal bifunctional electrocatalysts for water electrolysis in alkaline media,cobalt-doped molybdenum carbide@N-doped carbon nanosheets/nanotubes were fabricated by using C3N4 as the carbon source on a 3D porous nickel foam substrate.Benefiting from the optimized electronic structure and enhanced mass and charge transport,as well as the 3D conducting pathway,MoxCoy@N-CNSs/CNTs shows superior performance towards both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER)in an alkaline medium.The optimal electrocatalyst is Mo2Co1@N-CNSs/CNTs,which reveals a current density of 10 mA cm^-2 at the low overpotentials of 99 mV and 300 mV for the HER and OER,respectively,and a relatively low cell voltage(1.63 V)for the overall water electrolysis.The method of optimizing the composition and nanostructure of a material provides a new avenue for the development and utilization of high-performance electrocatalysts.
基金supported by the National Natural Science Foundation of China(21575134,21633008,21773224)National Key R&D Program of China(2016YFA0203200)K.C.Wong Education Foundation~~
文摘Catalysts play decisive roles in determining the energy conversion efficiencies of energy devices.Up to now,various types of nanostructured materials have been studied as advanced electrocatalysts.This review highlights the application of one‐dimensional(1D)metal electrocatalysts in energy conversion,focusing on two important reaction systems-direct methanol fuel cells and water splitting.In this review,we first give a broad introduction of electrochemical energy conversion.In the second section,we summarize the recent significant advances in the area of 1D metal nanostructured electrocatalysts for the electrochemical reactions involved in fuel cells and water splitting systems,including the oxygen reduction reaction,methanol oxidation reaction,hydrogen evolution reaction,and oxygen evolution reaction.Finally,based on the current studies on 1D nanostructures for energy electrocatalysis,we present a brief outlook on the research trend in 1D nanoelectrocatalysts for the two clean electrochemical energy conversion systems mentioned above.
文摘Efficient,stable,and noble‐metal‐free electrocatalysts for both the oxygen evolution reaction and the hydrogen evolution reaction are highly imperative for the realization of low‐cost commercial water‐splitting electrolyzers.Herein,a cost‐effective and ecofriendly strategy is reported to fabricate coral‐like FeNi(OH)x/Ni as a bifunctional electrocatalyst for overall water splitting in alkaline media.With the assistance of mild corrosion of Ni by Fe(NO3)3,in situ generated FeNi(OH)x nanosheets are intimately attached on metallic coral‐like Ni.Integration of these nanosheets with the electrodeposited coral‐like Ni skeleton and the supermacroporous Ni foam substrate forms a binder‐free hierarchical electrode,which is beneficial for exposing catalytic active sites,accelerating mass transport,and facilitating the release of gaseous species.In 1.0 mol L^-1 KOH solution,a symmetric electrolyzer constructed with FeNi(OH)x/Ni as both the anode and the cathode exhibits an excellent activity with an applied potential difference of 1.52 V at 10 mA cm^-2,which is superior to that of an asymmetric electrolyzer constructed with the state‐of‐the‐art RuO2‐PtC couple(applied potential difference of 1.55 V at 10 mA cm^-2).This work contributes a facile and reliable strategy for manufacturing affordable,practical,and promising water‐splitting devices.
基金the financial support from Chinese Scholarship Council (CSC)the support from Australian Research Council (ARC) Future Fellowship scheme
文摘The generation of hydrogen through the electrolysis of water has attracted attention as a promising way to produce and store energy using renewable energy sources.In this process,a catalyst is very important to achieve a high‐energy conversion efficiency for the electrolysis of water.A good catalyst for water electrolysis should exhibit high catalytic activity,good stability,low cost and good scalability.Much research has been devoted to developing efficient catalysts for both the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER).Traditionally,it has been accepted that a material with high crystallinity is important to serve as a good catalyst for HER and/or OER.Recently,catalysts for HER and/or OER in the electrolysis of water splitting based on amorphous materials have received much interest in the scientific community owing to the abundant unsaturated active sites on the amorphous surface,which form catalytic centers for the reaction of the electrolysis of water.We summarize the recent advances of amorphous catalysts for HER,OER and overall water splitting by electrolysis and the related fundamental chemical reactions involved in the electrolysis of water.The current challenges confronting the electrolysis of water and the development of more efficient amorphous catalysts are also discussed.
文摘Two-dimensional(2D)carbon nitride(CN)photocatalysts are attracting extensive attention owing to their excellent photocatalytic properties.In this study,we successfully prepared CN materials with heterogeneous structures via hydrothermal treatment,high-temperature roasting,ball milling,sintering,and other processes.Benefitting from interface interactions in hybrid architectures,the CN photocatalysts exhibited high photocatalytic activity.The rate of hydrogen production using these CN photocatalysts reached 17028.82μmol h^(−1)g^(−1),and the apparent quantum efficiency was 11.2%at 420 nm.The ns-level time-resolved photoluminescence(PL)spectra provided information about the time-averaged lifetime of fluorescence charge carriers;the lifetime of the charge carriers causing the fluorescence of CN reached 9.99 ns.Significantly,the CN photocatalysts displayed satisfactory results in overall water splitting without the addition of sacrificial agents.The average hydrogen and oxygen production rates were 270.95μmol h^(−1)g^(−1)and 115.21μmol h^(−1)g^(−1)in 7 h,respectively,which were promising results for the applications of the catalysts in overall water splitting processes.We investigated the high efficiency of the prepared CN photocatalysts via a series of tests(UV-vis diffuse reflectance spectroscopy,photocurrent response measurements,PL emission spectroscopy,time-resolved PL spectroscopy,and Brunauer-Emmett-Teller analysis).Furthermore,the Mott-Schottky plot and current-voltage curve were acquired via electrochemical tests.The fabricated CN photocatalyst had a small p-n junction in its heterogeneous structure,which further enhanced its photocatalytic efficiency.Therefore,this work can promote the development of CN photocatalysts.
文摘Step-scheme(S-scheme)heterojunctions in photocatalysts can provide novel and practical insight on promoting photogenerated carrier separation.The latter is critical in controlling the overall efficiency in one-step photoexcitation systems.In this study,a nanosized BiVO4/Bi0.6Y0.4VO4 solid solution was prepared by a coprecipitation method following with hydrothermal or calcination processes.The S-scheme heterojunction was fabricated by in-situ pressure-induced transformations of bismuth vanadate from the tetragonal zircon phase to the monoclinic scheelite phase,which led to the formation of BiVO4 nanoparticles with a diameter of approximately 5 nm on the surface of BiVO_(4)/Bi_(0.6)Y_(0.4)VO_(4)/Bi_(0.6)Y_(0.4)VO_(4) with S-scheme heterojunctions showed significantly enhanced photocatalytic overall water splitting activity compared with using bare BiVO_(4)/Bi_(0.6)Y_(0.4)VO_(4).Characterization of the carrier dynamics demonstrated that a superior carrier separation through S-type heterojunctions might have caused the enhanced overall water splitting(OWS)activity.Surface photovoltage spectra and the results of selective photodeposition experiments indicated that the photogenerated holes mainly migrated to the BiVO4 nanoparticles in the heterojunction.This confirmed that the charge transfer route corresponds to an S-scheme rather than a type-II heterojunction mechanism under light illumination.This study presents a facile and efficient strategy to construct S-scheme heterojunctions through a pressure-induced phase transition.The results demonstrated that S-scheme junctions composed of different crystalline phases can boost the carrier separation capacity and eventually improve the photocatalytic OWS activity.
基金supported by the National Natural Science Foundation of China(21376105,21576113)~~
文摘Designing low-cost, highly efficient, and stable bifunctional electrocatalysts for both hydrogen evolution reaction(HER) and oxygen evolution reaction(OER) is of vital significance for water splitting.Herein, three-dimensional lily-like CoNi_2S_4 supported on nickel foam(CoNi_2S_4/Ni) has been fabricated by sulfuration of the Co–Ni precursor. As expected, CoNi_2S_4/Ni possesses such outstanding electrocatalytic properties that it requires an overpotential of only 54 mV at 10 mA cm^(-2) and 328 mV at 100 mA cm^(-2) for HER and OER, respectively. Furthermore, by utilizing the CoNi_2S_4/Ni electrodes as bifunctional electrocatalysts for overall water splitting, a current density of 10 mA cm^(-2) can be obtained at a voltage of only 1.56 V.
文摘When a proton reduction cocatalyst is loaded on an n-type semiconductor for photocatalytic overall water splitting(POWS),the location of water oxidation sites is generally considered at the surface of the semiconductor due to upward band-bending of n-type semiconductor which may ease the transfer of the photogenerated holes to the surface.However,this is not the case for Pt/SrTiO_(3),a model semiconductor based photocatalyst for POWS.It was found that the photogenerated holes are more readily accumulated at the interface between Pt cocatalyst and SrTiO_(3) photocatalyst as probed by photo-oxidative deposition of PbO_(2),indicating that the water oxidation sites are located at the interface between Pt and SrTiO_(3).Electron paramagnetic resonance and scanning transmission electron microscope studies suggest that the interfacial oxygen atoms between Pt and SrTiO_(3) in Pt/SrTiO_(3) after POWS are more readily lost to form oxygen vacancies upon vacuum heat treatment,regardless of Pt loading by photodeposition or impregnation methods,which may serve as additional support for the location of the active sites for water oxidation at the interface.Density functional theory calculations also suggest that the oxygen evolution reaction more readily occurs at the interfacial sites with the lowest overpotential.These experimental and theoretical studies reveal that the more active sites for water oxidation are located at the interface between Pt and SrTiO_(3),rather than on the surface of SrTiO_(3).Hence,the tailor design and control of the interfacial properties are extremely important for the achievement or improvement of the POWS on cocatalyst loaded semiconductor photocatalyst.
文摘Efficient and stable bifunctional electrocatalysts for water splitting is essential for producing hydrogen and alleviating huge energy consumption.Meanwhile,charge transfer engineering is an efficient approach to modulate the localized electronic properties of catalysts and tune the electrocatalytic performance.Herein,we tactfully fabricate PtFeNi alloys/NiFe layered double hydroxides(LDHs)heterostructure by an easily electrochemical way with a small amount of Pt.The experimental and theoretical results unravel that the charge transfer on the alloy clusters modulated by the defective substrates(NiFe LDHs),which synergistically optimizes the adsorption energy of the reaction intermediates.The electrocatalyst exhibits an ultra‐low overpotential of 81 and 243 mV at the current density of 100 mA cm^(–2) for hydrogen evolution and oxygen evolution,respectively.Furthermore,the overall water splitting indicates that PtFeNi alloys/NiFe LDHs presents an ultra‐low overpotential of 265 and 406 mV to reach the current density of 10 and 300 mA cm^(–2),respectively.It proves that the PtFeNi alloys/NiFe LDHs catalyst is an excellent dual‐function electrocatalyst for water splitting and promising for industrialization.This work provides a new electrochemical approach to construct the alloy heterostructure.The prepared heterostructures act as an ideal platform to investigate the charge re‐distribution behavior and to improve the electrocatalytic activity.
文摘Investigation of the charge dynamics and roles of cocatalysts is crucial for understanding the reaction of photocatalytic water splitting on semiconductor photocatalysts.In this work,the dynamics of photogenerated electrons in Ga_(2)O_(3) loaded with Cr_(2)O_(3)-Rh cocatalysts was studied using time-resolved mid-infrared spectroscopy.The structure of these Cr_(2)O_(3)-Rh cocatalysts was identified with high-resolution transmission electron microscopy and CO adsorption Fourier-transform infrared spectroscopy,as Rh particles partly covered with Cr_(2)O_(3).The decay dynamics of photogenerated electrons reveals that only the electrons trapped by the Rh particles efficiently participate in the H2 evolution reaction.The loaded Cr_(2)O_(3) promotes electron transfer from Ga_(2)O_(3) to Rh,which accelerates the electron-consuming reaction for H2 evolution.Based on these observations,a photocatalytic water-splitting mechanism for Cr_(2)O_(3)-Rh/Ga_(2)O_(3) photocatalysts has been proposed.The elucidation of the roles of the Cr_(2)O_(3)-Rh cocatalysts aids in further understanding the reaction mechanisms of photocatalytic water splitting and guiding the development of improved photocatalysts.
文摘Exploring low-cost and highly active photocatalysts is very urgent to accomplish complete removal of phenolic contaminants and overcome the limitations of the existing photocatalysts.In this study,we designed and synthesized noble metal-free TiO2 photocatalysts by introducing bismuth nanoparticles as modifiers of a TiO2 single crystal(Bi-SCTiO2).The Bi-SCTiO2 can make full use of the synergistic effect of a small band overlap and low charge carrier density(Bi)with a high conductivity(single crystal),significantly boosting the separation and migration of the photogenerated charge pairs.Therefore,the Bi-SCTiO2 photocatalyst exhibits a significantly enhanced degradation rate(12 times faster)of 4-nitrophenol than a TiO2 single crystal under simulated sunlight irradiation.Notably,the complete removal of phenolic contaminants is achieved in various water matrices,which not only successfully overcomes the incomplete degradation in many reported photocatalytic systems,but also manifests a significant practical potential for sewage disposal.Therefore,this work presents a new insight in designing and constructing noble metal-free decorated semiconductor single-crystal photocatalysts with excellent activity and cyclability.
文摘The paper presents the research for the purpose of selecting microorganisms into the production process of "chao" to improve the quality of "chao" products and ensure food safety. Several analytical methods such as determination of formal nitrogen, determination of the protease hydrolysis activity, sensory evaluation method, experimental procedure, methods of analysis and processing of empirical data were used in this study. The findings showed that two out of four selected microorganism strains (one strain of fungi and three strains of bacteria denoted NM1, VK1, VK2, VK3, respectively) were the most appropriate for the cooperation among them and the production of %hao", which were coded NM1 and VK1. The suitable mixing proportion of strains of NM1 and VK1 was determined at 1:1.25, compatible with the 1:100 ratio of the varieties of microorganisms (in powder form) to tofu.
基金Project(51178468) supported by the National Natural Science Foundation of ChinaProject(2010bsxt07) supported by the Doctoral Dissertation Innovation Fund of Central South University,China
文摘Based on the upper bound theorem of limit analysis,the factor of safety for shallow tunnel in saturated soil is calculated in conjunction with the strength reduction technique.To analyze the influence of the pore pressure on the factor of safety for shallow tunnel,the power of pore pressure is regarded as a power of external force in the energy calculation.Using the rigid multiple-block failure mechanism,the objective function for the factor of safety is constructed and the optimal solutions are derived by employing the sequential quadratic programming.According to the results of optimization calculation,the factor of safety of shallow tunnel for different pore pressure coefficients and variational groundwater tables are obtained.The parameter analysis shows that the pore pressure coefficient and the location of the groundwater table have significant influence on the factor of safety for shallow tunnel.