Zinc-doped g-C_3N_4/BiVO_4 as a Z-scheme photocatalyst system for water splitting under visible light

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 samples.It was determined that more Zn?N bonds could be formed on the surface of g‐C3N4by impregnation,which could facilitate charge transfer.

Recent advances and perspectives in cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) fixation

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 topic.Hence,various types of photocatalysts have been developed successively to meet the requirements of these photocatalysis.Among 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 barrier.In this review,we first present the working principles of cobalt‐based heterogeneous catalysts for photocatalytic water splitting,CO_(2) reduction,and N_(2) fixation.Second,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 catalysts.Finally,the central challenges and possible improvements of cobalt‐based photocatalysis in the future are presented.The purpose of this review is to summarize the past experience and lessons,and provide reference for the further development of cobalt‐based photocatalysis technology.

Preparation of nanostructure silver powders by mechanical decomposing and mechanochemical reduction of silver oxide

The mechanical decomposing and mechanochemical reductions of silver oxide for preparation of nanocrystalline silver powders by high planetary ball mill was investigated. XRD and HRSEM techniques were used to characterize the structural evolution and morphological changes of products. The results show that the nanostructured silver with an average crystallite size of 14 nm and internal strain of 0.75% is synthesized by mechanical decomposing of Ag2O after 95 h milling. While, the product of mechanochemical reduction of silver oxide using graphite after 22 h milling is nanostructured silver with an average crystallite size of 28 nm and internal strain of 0.44%.

MXenes for electrocatalysis applications:Modification and hybridization

Two-dimensional carbides,nitrides,and carbonitrides(MXenes)play important roles in promoting the development of sustainable energy because they have abundant reactive sites on their surfaces.An increasing number of MXenes with diverse elements and composites have been predicted and synthesized for electrocatalysis applications since the first report of a Ti-Mo-based MXene for the hydrogen evolution reaction(HER).Herein,we summarize the progress of MXene-based electrocatalysts for the HER,the oxygen evolution reaction,and the oxygen reduction reaction,including regulated pristine MXenes and modified hybrid MXenes,from both theoretical and experimental perspectives.A brief overview on MXene synthesis is presented first,accompanied by a discussion on the relationship between electrocatalytic properties and M,X,T,vacancies,and morphologies.After reviewing strategies in terms of atom substitution,functional modification,defect engineering,and morphology control,we emphasize the construction of heterojunctions between MXenes and other nanostructures,such as metal nanoparticles,oxides,hydroxides,sulfides,and phosphides.We finally discuss prospects for the future development of MXene-based electrocatalysts.

Study on Water-Soluble Organic Reducing Substances: II. Organic Reducing Substances Produced from Anaerobic Decomposition of Milk Vetch (Astragalus sinicus L.)

The characteristics of electric charge and molecular weight distribution,oxidation-reduction regimes,e.g.Eh and amounts of organic reducing substances produced by milk vetch during anaerobic decomposition process,were studied by using electrochemical methods.Interaction between soils and organic reducing substances was also observed.The results indicate that the organic reducing substances were mainly the organic compounds with negative and amphoteric charges,which were distributed in two groups at anodic peak potentials of 0.25 and 0.69 volt in differential pulse voltammograms,respectively.Their apparent molecular weights are all less than 700 daltons,in which those active in oxidation-reducion reaction were distributed in the fraction with apparent molecular weight less than 200 daltons.The organic reduction substances can be oxidized by manganese oxides in their interaction with soils.

Highly efficient mixed-metal spinel cobaltite electrocatalysts for the oxygen evolution reaction

Cation substitution in spinel cobaltites(e.g.,ACo2O4,in which A=Mn,Fe,Co,Ni,Cu,or Zn)is a promising strategy to precisely modulate their electronic structure/properties and thus improve the corresponding electrochemical performance for water splitting.However,the fundamental principles and mechanisms are not fully understood.This research aims to systematically investigate the effects of cation substitution in spinel cobaltites derived from mixed-metal-organic frameworks on the oxygen evolution reaction(OER).Among the obtained ACo2O4 catalysts,FeCo2O4 showed excellent OER performance with a current density of 10 mA·cm^-2 at an overpotential of 164 mV in alkaline media.Both theoretical calculations and experimental results demonstrate that the Fe substitution in the crystal lattice of ACo2O4 can significantly accelerate charge transfer,thereby achieving enhanced electrochemical properties.The crystal field of spinel ACo2O4,which determines the valence states of cations A,is identified as the key factor to dictate the OER performance of these spinel cobaltites.

Rational design and precise manipulation of nano‐catalysts

Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.

Stabilization of S_(3)O_(4) at high pressure:implications for the sulfur-excess paradox

The amount of sulfur in SO2 discharged in volcanic eruptions exceeds that available for degassing from the erupted magma.This geological conun drum,known as the"sulfur excess",has been the subject of considerable interests but remains an open question.Here,in a systematic computational investigation of sulfur-oxygen compounds under pressure,a hitherto unknown S_(3)O_(4) compound containing a mixture of sulfur oxidation states+11 and+IV is predicted to be stable at pressures above 79 GPa.We speculate that S_(3)O_(4) may be produced via redox reactions involving subducted S-bearing minerals(e.g.,sulfates and sulfides)with iron and goethite under high-pressure conditions of the deep lower mantle,decomposing to SO2 and S at shallow depths.S_(3)O_(4) may thus be a key intermediate in promoting decomposition of sulfates to release SO2,offering an alter native source of excess sulfur released during explosive eruptions.These findings provide a possible resolution of the"excess sulfur degassing"paradox and a viable mechanism for the exchange of S between Earth's surface and the lower mantle in the deep sulfur cycle.