摘要：As a clean and renewable future energy source, hydrogen fuel can be produced via solar water splitting. Two-dimensional (2D) black phosphorene (black-P) can harvest visible light due to the desirable band gap, which promises it as a metal-free photocatalyst. However, black-P can be only used to produce hydrogen since the oxidation potential of water locates lower than the position of the valence band maximum. To improve the photocatalytic performance of black-P, here, using black-P and blue phosphorene (blue-P) monolayers, we propose a 2D van der Waals (vdW) heterojunction. Theoretical results, including the band structures, density of states, Bader charge population, charge density di erence, and optical absorption spectra, clearly reveal that the visible light absorption ability is obviously improved, and the band edge alignment of the proposed vdW heterojunction displays a typical type-II feature to effectively separate the photogenerated carriers. At the same time, the built-in interfacial electric field prevents the electron-hole recombination. These predictions suggest that the examined phosphorene-based vdW heterojunction is an efficient photocatalyst for solar water splitting.

摘要：Tandem water electrolysis for the transformation of universal feedstock to value-added chemicals integrated with hydrogen generation and in situ utilization is a promising approach to address the economic challenges of electrochemical hydrogen evolution and ***,we present the controllable electrocatalytic deuteration of halides using inexpensive and reusable heavy water(D2 O)as a D-source for the preparation of valuable D-labelled chemicals and pharmaceuticals under mild *** electrochemical deuteration method with high efficiency and selectivity furnishes a series of D-labelled chemicals and pharmaceuticals in high yields with excellent *** reaction efficiency and selectivity,that is,the precise substitution of deuterium atoms at different halogen positions,can be tuned by varying the applied *** results show the great potential of green and economical electrocatalytic methods for producing value-added fine chemicals in addition to hydrogen evolution.

摘要：Charge separation is a crucial problem in *** used a wet‐chemical method to synthesize asymmetrically tipped PdS‐CdSe‐seeded CdS(CdSe@CdS)‐Au nanorod(NR)heterostructures(HCs).In these HCs,electrons and holes are rapidly separated and transported to opposite ends of the NRs by internal electric *** ultraviolet‐visible absorption spectra showed strong electronic coupling between both tips and the CdS ***‐CdSe@CdS‐Au achieved a H2production rate of ca.1100?mol in5h;this is two orders of magnitude greater than the rate achieved with Au‐CdSe@CdS NRs with only one ***‐CdSe@CdS‐Au NRs can withstand4h of photoirradiation,compared to1.5h for CdSe@CdS NRs,indicating that the photostability of PdS‐CdSe@CdS‐Au is much better than that of *** greatly improved photocatalytic activity and stability are attributed to efficient charge separation and rapid charge transport in the PdS‐CdSe@CdS‐Au HCs.

摘要：Common solar-driven photoelectrochemical(PEC) cells for water splitting were designed by using semiconducting photoactive materials as working photoelectrodes to capture sunlight. Due to the thermodynamic requirement of 1.23 eV and kinetic energy loss of about 0.6 eV, a photo-voltage of 1.8 V produced by PEC cells is generally required for spontaneous water splitting. Therefore, the minimum bandgap of1.8 eV is demanded for photoactive materials in single-photoelectrode PEC cells, and the bandgap of about 1 eV for back photoactive materials is appropriate in tandem PEC cells. All these PEC cells cannot effectively utilize the infrared light from 1250 to 2500 nm. In order to realize the full spectrum utilization of solar light, here, we develop a solar-driven PEC water splitting system integrated with a thermoelectric device. The key feature of this system is that the thermoelectric device produces a voltage as an additional bias for the PEC system by using the temperature difference between the incident infrared-light heated aqueous electrolyte in the PEC cell as the hot source and unirradiated external water as the cold source. Compared to a reference PEC system without the thermoelectric device, this system has a significantly improved overall water splitting activity of 1.6 times and may provide a strategy for accelerating the application of full spectrum solar light-driven PEC cells for hydrogen production.

摘要：Most biological photoredox reactions occur in sophisticated molecular assemblies consisting of highly organized light-harvesting moieties and catalytic *** these prototypes by creating supramolecular assemblies could be a potentially viable approach toward artificial *** self-assembled organic materials are known to carry out water splitting reactions,developing self-assembled organic materials for photocatalytic overall water splitting still remains a critical ***,we first demonstrate that crystalline organic nanosheets assembled from linear oligo(phenylene butadiynylene)(OPB)are able to catalyze overall water splitting under visible light *** investigations reveal that the photocatalytic activity of self-assembled organic structures is closely related to the crystalline structure along with the corresponding electronic *** disorders in OPB nanosheets and extrinsic factors such as adsorbed water molecules will induce the formation of electron traps which can make the OPB nanosheets thermodynamically unfavorable for photocatalytic overall water *** deactivation mechanism unveiled in this study provides crucial insights into the assembling of artificial organic materials for future solar-to-chemical energy conversion.

摘要：The rational design of efficient and stable carbon-based electrocatalysts for oxygen reduction and oxygen evolution reactions is crucial for improving energy density and long-term stability of rechargeable zinc-air batteries(ZABs).Herein,a general and controllable synthesis method was developed to prepare three-dimensional(3D)porous carbon composites embedded with diverse metal phosphide nanocrystallites by interfacial coordination of transition metal ions with phytic acid-doped polyaniline networks and subsequent *** acid as the dopant of polyaniline provides favorable anchoring sites for metal ions owing to the coordination ***,adjusting the concentration of adsorbed cobalt ions can achieve the phase regulation of transition metal ***,with abundant cobalt phosphide nanoparticles and nitrogen-and phosphorus-doping sites,the obtained carbon-based electrocatalysts exhibited efficient electrocatalytic activities toward oxygen reduction and evolution ***,the fabricated ZABs exhibited a high energy density,high power density of 368 mW cm^(-2),and good cycling/mechanical stability,which could power water splitting for integrated device fabrication with high gas yields.

摘要：It is a great challenge to develop highly active oxygen evolution reaction(OER)electrocatalysts with superior *** this study,a NiFe layered double hydroxidedecorated phosphide(NiFe LDH@CoP/NiP_(3))was constructed to display satisfactory OER activity and good stability for water splitting in alkaline *** an overpotential of 300 mV,NiFe LDH@CoP/NiP_(3) achieved a current density of 82 mA cm^(-2) for the OER,which was 9.1 and 2.3 times that of CoP/NiP_(3) and NiFe LDH,***,the reconstruction behavior,during which oxyhydroxides formed,was studied by a combination of X-ray photoelectron spectroscopy,Raman spectroscopy,and scanning electron microscopy.A synergistic effect between NiFe LDH and CoP/NiP_(3) was also observed for the hydrogen evolution ***,when NiFe LDH@CoP/NiP_(3) acted as both the cathode and anode for overall water splitting,a high current density of 100 mA cm^(-2) was maintained for more than 275 *** addition,under Xe light irradiation,a solar-to-hydrogen efficiency of 9.89% was achieved for solar-driven water *** work presents the coupling of different active compositions,and can provide a reference for designing bifunctional electrocatalysts.

摘要：Efficient,low-cost,and stable electrocatalysts for water splitting are highly ***,three-dimensional(3D)Ni_(2)P nanosheet arrays were fabricated and simultaneously modulated by heterostructure engineering and Mn doping(Mn-doped Ni_(2)O_(3)/Ni_(2)P and Mn-doped Ni_(x)S_(y)/Ni_(2)P)via a facile hydrothermal reaction and subsequent phosphorization and *** to the Mn doping,synergistic effect in the heterostructures,and abundantly exposed active sites from the 3D-nanosheet arrays,Mn-doped Ni_(2)O_(3)/Ni_(2)P and Mn-doped Ni_(x)S_(y)/Ni_(2)P exhibit excellent properties for the hydrogen evolution reaction(HER)and oxygen evolution reaction(OER),*** former achieves an excellent current density of-10 mA cm^(-2) at a low overpotential of 104 mV for HER,while the latter attains 100 mA cm^(-2) for OER at an ultralow overpotential of 290 mV and exhibits superior stability at 50 mA cm^(-2) for 160 ***,the Mndoped Ni_(2)O_(3)/Ni_(2)P//Mn-doped Ni_(x)S_(y)/Ni_(2)P couple show high overall-water-splitting activity with a cell voltage of 1.65 V at 10 mA cm^(-2) and outstanding durability at 50 mA cm^(-2) for 120 h in an alkaline *** work presents an effective strategy to design and synthesize low-cost and highly active non-noble metal electrocatalysts for overall water splitting through the simultaneous application of heterostructure engineering,foreign-metal-atom doping,and a 3Dnanoarray *** strategy brings a paradigm shift toward the mass production of low-cost non-noble metal electrocatalysts for renewable energy devices.

摘要：Designing and constructing bifunctional electrocatalysts with high efficiency,high stability and low cost for overall water splitting to produce clean hydrogen fuel is attractive but highly *** we constructed puffed quaternary FexCoyNi1-x-yP nanoarrays as bifunctional electrodes for robust overall water *** iron was used as the modulator to manipulate the electron density of NiCoP nanoarray,which could increase the positive charges of metal(Ni and Co)and P *** resultant electronic structure of FexCoyNi1-x-yP was supposed to balance the adsorption and desorption of H and accelerate the oxygen evolution reaction(OER)***,the morphological structure of FexCoyNi1-x-yP was modulated through the kinetically controlled alkaline etching by using the amphoteric features of initial FeCoNi hydroxide *** resultant puffed structure has rich porosity,cavity and defects,which benefit the exposure of more active sites and the transport of mass/*** a result,the cell integrated with the puffed quaternary FexCoyNi1-x-yP nanoarrays as both the cathode and anode only requires the overpotentials of 25 and 230 mV for hydrogen evolution reaction(HER)and OER at the current density of 10 mA cm^-2 in alkaline media and a cell voltage of 1.48 V to drive the overall water ***,the puffed FexCoyNi1-x-yP demonstrates remarkable durability for continuous electrolysis even at a large current density of 240 mA cm^-2.

摘要：The ternary cobalt-nickel-iron phosphide nanocubes (P-Co0.9Ni0.9Fe1.2 NCs) with high intrinsic activity, conductivity, defect concentration and optimized ratio have been realized through a facile phosphorization treatment using ternary cobalt-nickel-iron nanocubes of Prussian blue analogs (PBA) as a precursor. The scanning electron microscopy and transmission electron microscopy results show that the P-Co0.9Ni0.9Fe1.2 NCs maintain a cubic structure with a rough surface, implying the rich surface defects as exposed active sites. The thermal phosphorization of the ternary PBA precursor not only provids carbon doping but also leads to the in situ construction of surface defects on the NCs. The carbon doping from the PBA precursor lowers the charge transfer resistance and optimizes the electronic transformation. The synergistic effect among the ternary metal ions and rich defects contributes to the enhanced electrocatalytic performance . The P-Co0.9Ni0.9Fe1.2NCs achieve low overpotentials of -200.7 and 273.1 mV at a current density of 10 mA cm^-2 for the hydrogen evolution reaction and the oxygen evolution reaction, respectively. The potential of overall water splitting reaches 1.52 V at a current density of 10 mA cm^-2. The longterm stability of the electrocatalysts was also evaluated. This work provides a facile method to design efficient transitionmetal- based bifunctional electrocatalysts for overall water splitting.