摘要：Hierarchical nanostructures have attracted widespread interest owing to their unique properties compared to their bulk counterparts. Thus, they are considered promising electrocatalytic materials. In this work, a novel hierarchical porous nanocomposite of cobalt phosphide nanocage@ferric-zinc mixed-metal phosphide nanotubes(denoted Co P@Zn Fe P) was fabricated using a self-assembly approach. Because of their structural and compositional merits, the as-prepared phosphide hybrids have abundant catalytic active sites and high porosity for facile mass diffusion. In an alkaline electrolyte, the CoP@ZnFeP flower-like hybrids displayed enhanced catalytic activity for the hydrogen evolution reaction and the oxygen evolution reaction compared with a mechanical mixture of Co P and Zn Fe P nanoparticles. The CoP@ZnFeP hierarchical nanocomposites also showed excellent activity for the overall water splitting reaction, yielding a water-splitting current of 10 mA/cm^2 on the application of just 1.6 V, as well as excellent durability(24-h long-term operation) in a two-electrode system. Our design methodology may create opportunities to search for highly efficient and robust non-precious metal catalysts with applications in high-performance energy conversion and storage devices.

摘要：Photocatalytic hydrogen(H2)evolution via water spilling over semiconductors has been considered to be one of the most promising strategies for sustainable energy supply in the future to provide non-pollution and renewable *** key to efficient conversion of solar-chemical energy is the design of an efficient structure for high charge separation and ***,cocatalysts are necessary in boosting photocatalytic H2 *** date,semiconductor photocatalysts have been modified by various cocatalysts due to the extended light harvest,enhanced charge carrier separation efficiency and improved *** review focuses on recent developments of cocatalysts in photocatalytic H2 evolution,the roles and mechanism of the cocatalysts are discussed in *** cocatalysts can be divided into the following categories:metal/alloy cocatalysts,metal phosphides cocatalysts,metal oxide/hydroxide cocatalysts,carbon-based cocatalysts,dual cocatalysts,Z-scheme cocatalysts and MOFs *** future research and forecast for photocatalytic hydrogen generation are also suggested.

摘要：A novel metal/semiconductor photocatalyst,Cu nanoparticles(NPs)modified TiO2 hollow spheres(Cu/TiO2),was designed for efficient photocatalytic overall water splitting(POWS)under both ultraviolet(UV)and visible(Vis)*** Cu/TiO2 photocatalyst possesses excellent POWS performance under Vis light at the highest level among the reported TiO2-based ***,the metal/semiconductor junction formed between Cu and TiO2 enables controlled water-oxidation product selectivity(H2O2 or O2)via different reaction pathways regulated by irradiation *** UV light,the electrons excited in TiO2 are captured by Cu NPs through the Cu/TiO2 Schottky interface for H2 production,with the photoholes in TiO2 producing H2O2 through a two-electron process;whilst under Vis light,Cu NPs act as plasmon to inject hot electrons to TiO2 for H2 production,while O2 is produced by hot holes on Cu NPs via a four-electron *** rational design of function-switchable metal/semiconductor junction may be helpful to understand the mechanisms for POWS with desired gas/liquid water-oxidation products.

摘要：The demanding all-in-one electrocatalyst system for oxygen reduction reaction(ORR), oxygen evolution reaction(OER) and hydrogen evolution reaction(HER) in zinc-air batteries or water splitting requires elaborate material manufacturing, which is usually complicated and *** interface engineering between MXene and highly active electrocatalytic species(CoS_(2)) is, herein, achieved by an in situ hydrothermal growth and facile sulfurization *** CoS_(2)@MXene electrocatalyst is composed by one-dimensional CoS_(2) nanowires and two-dimensional MXene nanosheets, which lead to a hierarchical structure(large specific surface area and abundant active sites), a spatial electron redistribution(high intrinsic activity), and high anchoring strength(superior performance stability). Therefore, the electrocatalyst achieves enhanced catalytic activity and longtime stability for ORR(a half-wave potential of 0.80 V), OER(an overpotential of 270 mV at 10 mA cm^(-2), i.e., η10= 270 mV)and HER(η10= 175 mV). Furthermore, the asymmetry water splitting system based on the CoS_(2)@MXene composites delivers a low overall voltage of 1.63 V at 10 mA cm^(-2). The solidstate zinc-air batteries using CoS_(2)@MXene as the air cathode display a small charge-discharge voltage gap(0.53 V at1 mA cm^(-2)) and superior stability(60 circles and 20-h continuous test). The energy interconversion between the chemical energy and electricity can be achieved by a self-powered system via integrating the water splitting system and quasisolid-state zinc-air batteries. Supported by in situ Raman analyses, the formation of cobalt oxyhydroxide species provides the active sites for water oxidation. This study paves apromising avenue for the design and application of multifunctional nanocatalysts.

摘要：The photocatalytic activity of a semiconductor‐based photocatalyst largely depends on the semiconductor’s intrinsic crystal and electronic *** have prepared two types of La and Cr co‐doped SrTiO3photocatalysts(SrTiO3(La,Cr))using the polymerized complex method(PCM)and sol‐gel hydrothermal method(SHM).Under?>420‐nm visible light irradiation,only the Pt‐loaded SrTiO3(La,Cr)prepared by the SHM showed efficient photocatalytic activities for both H2evolution in the presence of an I?sacrificial reagent and for Z‐scheme overall water splitting when it was coupled with the Pt‐loaded WO3in the presence of I?and IO3?as the shuttle redox *** superior photocatalytic activity of SrTiO3(La,Cr)prepared by the SHM has been ascribed to its more negative conduction‐band position,higher carrier concentration,and higher carrier mobility,demonstrating that the design and synthesis of an H2‐evolution photocatalyst with appropriate electronic properties is crucial for achieving Z‐scheme overall water splitting.

摘要：As the kinetically sluggish oxygen evolution reaction(OER)is considered to be a bottleneck in overall water splitting,it is necessary to develop a highly active and stable electrocatalyst to overcome this ***,we successfully fabricated a three-dimensional iron-dysprosium oxide co-regulated in-situ formed MOF-Ni arrays on carbon cloth(FeDy@MOF-Ni/CC)through a facile two-step hydrothermal *** studies demonstrate that the designed FeDy@MOF-Ni/CC catalyst requires an overpotential of only 251 mV to reach 10 mA cm-2 with a small Tafel slope of 52.1 mV ***,the stability declined by only 5.5%after 80 h of continuous testing in 1.0 M ***,a cell voltage of only 1.57 V in the overall water splitting system is sufficient to achieve 10 mA cm-2;this value is far better than that of most previously reported *** excellent catalytic performance originates from the unique 3D rhombus-like structure,as well as coupling synergies of Fe-Dy-Ni *** combination of lanthanide and transition metal species in the synthesis strategy may open entirely new possibilities with promising potential in the design of highly active OER electrocatalysts.

摘要：Solar‐driven conversion of carbon dioxide,water and nitrogen into high value‐added fuels(e.g.H_(2),CO,CH_(4),CH_(3)OH,NH_(3) and so on)is regarded as an environmental‐friendly and ideal route for relieving the greenhouse gas effect and countering energy crisis,which is an attractive and challenging ***,various types of photocatalysts have been developed successively to meet the requirements of these *** them,cobalt‐based heterogeneous catalysts emerge as one of the most promising photocatalysts that open up alluring vistas in the field of solar‐to‐fuels conversion,which can effectively enhance photocatalytic efficiency by extending light absorption range,promoting charge separation,providing active sites,and lowering reaction *** this review,we first present the working principles of cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) ***,five efficient strategies including surface modification,morphology modulation,crystallinity controlling,crystal engineering and doping,are discussed for improving the photocatalytic performance with different types cobalt‐based catalysts(cobalt nanoparticles and single atom,oxides,sulfides,phosphides,MOFs,COFs,LDHs,carbide,and nitrides).Third,we outline the applications for the state‐of‐the‐art photocatalytic CO_(2) reduction and water splitting,and nitrogen fixation over cobalt‐based heterogeneous ***,the central challenges and possible improvements of cobalt‐based photocatalysis in the future are *** purpose of this review is to summarize the past experience and lessons,and provide reference for the further development of cobalt‐based photocatalysis technology.

摘要：The development of highly potential electrocatalysts for acidic water electrolysis is particularly desirable for many energy‐related ***,we demonstrated a versatile strategy to activate and stabilize RuO_(2)‐based electrocatalyst for acidic water splitting by a trace of Pt,where Pt plays an essential role in promoting oxygen evolution reaction(OER),and can simultaneously act as the active site for hydrogen evolution reaction(HER).Compared with pure Ru oxide nanosheet assemblies(Ru ONAs),the“5%Pt‐containing”Ru ONAs(5%Pt‐Ru ONAs)achieve much enhanced OER activity in 0.5 and 0.05 mol/L H_(2)SO_(4),with much lower overpotentials of 227 and 234 mV at 10 mA cm^(‒2),*** and theoretical analyses reveal that the atomically dispersed Pt incorporating into RuO_(2)lattice is conducive to increasing the concentration of O vacancies,which effectively enhances the interaction with reaction intermediate and thus lowers the energy barrier for the formation of OOH*.Moreover,benefited from the presence of Pt,the formation of RuO_(2)is more achievable when proper annealing is *** addition to OER,due to the presence of active Pt,the HER performance of 5%Pt‐Ru ONAs can also be ensured,thereby realizing efficient acidic overall water ***,the excellent activity can also be achieved without sacrificing *** work highlights an attractive strategy for designing active and stable RuO_(2)‐based electrocatalysts for acidic overall water splitting.

摘要：A two‐step photocatalytic water splitting system,termed a“Z‐scheme system”,was achieved using Zn‐doped g‐C3N4for H2evolution and BiVO4for O2evolution with Fe2+/Fe3+as a shuttle redox mediator.H2and O2were evaluated simultaneously when the doping amount of zinc was10%.Moreover,Zn‐doped(10%)g‐C3N4synthesized by an impregnation method showed superior active ability to form the Z‐scheme with BiVO4than by in‐situ synthesis.X‐ray diffraction,UV‐Vis spectroscopy,scanning electron microscopy,and X‐ray photoelectron spectroscopy were used to characterize the *** was determined that more Zn?N bonds could be formed on the surface of g‐C3N4by impregnation,which could facilitate charge transfer.

摘要：Photoelectorchemical（PEC） water splitting is an attractive approach for producing sustainable and environment-friendly hydrogen. An efficient PEC process is rooted in appropriate semiconductor materials, which should possess small bandgap to ensure wide light harvest, facile charge separation to allow the generated photocharges migrating to the reactive sites and highly catalytic capability to fully utilize the separated photocharges. Proper electrode fabrication method is of equal importance for promoting charge transfer and accelerating surface reactions in the electrodes. Moreover,powerful characterization method can shed light on the complex PEC process and provide deep understanding of the rate-determining step for us to improve the PEC systems further. Targeting on high solar conversion efficiency, here we provide a review on the development of PEC water splitting in the aspect of materials exploring, fabrication method and characterization. It is expected to provide some fundamental insight of PEC and inspire the design of more effective PEC systems.