Integration of morphology and electronic structure modulation on cobalt phosphide nanosheets to boost photocatalytic hydrogen evolution from ammonia borane hydrolysis

The controllable and safe hydrogen storage technologies are widely recognized as the main bottleneck for the accomplishment of sustainable hydrogen energy.Ammonia borane(AB)has regarded as a competitive candidate for chemical hydrogen storage.However,developing efficient yet high-performance catalysts towards hydrogen evolution from AB hydrolysis remains an enormous challenge.Herein,cobalt phosphide nanosheets are synthesized by a facile salt-assisted along with low-temperature phosphidation strategy for simultaneously modulating its morphology and electronic structure,and function as hydrogen evolution photocatalysts.Impressively,the Co_(2)P nanosheets display extraordinary performance with a record high turnover frequency of 44.9 min^(-1),outperforming most of the noble-metal-free catalysts reported to date.This remarkable performance is attributed to its desired nanosheets structure,featuring with high specific surface area,abundant exposed active sites,and short charge diffusion paths.Our findings provide a novel strategy for regulating metal phosphides with desired phase structure and morphology for energy-related applications and beyond.

A general synthetic strategy for N, P co-doped graphene supported metal-rich noble metal phosphides for hydrogen generation

The exploitation of electrocatalysts with high activity and durability for HER is desirable for future energy systems,but it is still a challenge.NMPs have attracted increasing attentions,but the preparation process often needs toxic regents or dangerous reaction conditions.Herein,we develop a general green method to fabricate metal-rich NMPs anchored on NPG through pyrolyzing DNA cross-linked complexes.The obtained Ru_(2) P-NPG exhibits an ultrasmall overpotential of 7 mV at 10 mA cm^(2) and ultralow Tafel slope of 33 mV dec^(-1) in 1.0 mol L?1 KOH,even better than that of commercial Pt/C.In addition,Ru 2 P-NPG also shows low overpotentials of 29 and 78 mV in 0.5 mol L^(-1) H_(2)SO_(4) and 1.0 mol L^(-1) PBS,respectively.The superior activity can be attributed to the ultrafine dispersion of Ru 2 P nanoparticles for more accessible sites,more defects formed for abundant active sites,the two-dimensional plane structure for accelerated electron transfer and mass transport,as well as the regulation of electron distribution of the catalyst.Moreover,the synthetic method can also be applied to prepare other metal-rich noble metal phosphides(Pd_(3)P-NPG and Rh_(2)P-NPG),which also exhibits high activity for HER.This work provides an effective strategy for designing NMP-based electrocatalysts.

In situ formation of multiple catalysts for enhancing the hydrogen storage of MgH_(2) by adding porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres

MgH_(2) is considered one of the most promising hydrogen storage materials because of its safety,high efficiency,high hydrogen storage quantity and low cost characteristics.But some shortcomings are still existed:high operating temperature and poor hydrogen absorption dynamics,which limit its application.Porous Ni_(3)ZnC_(0.7)/Ni loaded carbon nanotubes microspheres(NZC/Ni@CNT)is prepared by facile filtration and calcination method.Then the different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%)is added to the MgH_(2) by ball milling.Among the three samples with different amount of NZC/Ni@CNT(2.5,5.0 and 7.5 wt%),the MgH_(2)-5 wt%NZC/Ni@CNT composite exhibits the best hydrogen storage performances.After testing,the MgH_(2)-5 wt%NZC/Ni@CNT begins to release hydrogen at around 110℃ and hydrogen absorption capacity reaches 2.34 wt%H_(2) at 80℃ within 60 min.Moreover,the composite can release about 5.36 wt%H_(2) at 300℃.In addition,hydrogen absorption and desorption activation energies of the MgH_(2)-5 wt%NZC/Ni@CNT composite are reduced to 37.28 and 84.22 KJ/mol H_(2),respectively.The in situ generated Mg_(2)NiH_(4)/Mg_(2)Ni can serve as a"hydrogen pump"that plays the main role in providing more activation sites and hydrogen diffusion channels which promotes H_(2) dissociation during hydrogen absorption process.In addition,the evenly dispersed Zn and MgZn2 in Mg and MgH_(2) could provide sites for Mg/MgH_(2) nucleation and hydrogen diffusion channel.This attempt clearly proved that the bimetallic carbide Ni_(3)ZnC_(0.7) is a effective additive for the hydrogen storage performances modification of MgH_(2),and the facile synthesis of the Ni_(3)ZnC_(0.7)/Ni@CNT can provide directions of better designing high performance carbide catalysts for improving MgH_(2).

Achieving Negatively Charged Pt Single Atoms on Amorphous Ni(OH)_(2)Nanosheets with Promoted Hydrogen Absorption in Hydrogen Evolution

Single-atom(SA)catalysts with nearly 100%atom utilization have been widely employed in electrolysis for decades,due to the outperforming catalytic activity and selectivity.However,most of the reported SA catalysts are fixed through the strong bonding between the dispersed single metallic atoms with nonmetallic atoms of the substrates,which greatly limits the controllable regulation of electrocatalytic activity of SA catalysts.In this work,Pt-Ni bonded Pt SA catalyst with adjustable electronic states was successfully constructed through a controllable electrochemical reduction on the coordination unsaturated amorphous Ni(OH)_(2)nanosheet arrays.Based on the X-ray absorption fine structure analysis and first-principles calculations,Pt SA was bonded with Ni sites of amorphous Ni(OH)_(2),rather than conventional O sites,resulting in negatively charged Pt^(δ-).In situ Raman spectroscopy revealed that the changed configuration and electronic states greatly enhanced absorbability for activated hydrogen atoms,which were the essential intermediate for alkaline hydrogen evolution reaction.The hydrogen spillover process was revealed from amorphous Ni(OH)_(2)that effectively cleave the H-O-H bond of H_(2)O and produce H atom to the Pt SA sites,leading to a low overpotential of 48 mV in alkaline electrolyte at-1000 mA cm^(-2)mg^(-1)_(Pt),evidently better than commercial Pt/C catalysts.This work provided new strategy for the control-lable modulation of the local structure of SA catalysts and the systematic regulation of the electronic states.

Absorption characteristics,model,and molecular mechanism of hydrogen sulfide in morpholine acetate aqueous solution

The solubility of H_(2)S was measured in solutions of N-butyl-N-methylmorpholine acetate([Bmmorp][Ac])containing 20%-40%(mass)water at experimental temperatures ranged from 298.15 to 328.15 K and pressures up to 320 k Pa.The total solubility of H_(2)S increased with higher temperatures,lower pressures,and reduced water content.The reaction equilibrium thermodynamic model was used to correlate the solubility data.The results indicate that the chemical reaction equilibrium constant decrease with increasing water content and temperature,whereas Henry constant increase with increasing water content and temperature.Compared with other ionic liquids,H_(2)S exhibits a higher physical absorption enthalpy and a lower chemical absorption enthalpy in[Bmmorp][Ac]aqueous solution.This suggests that[Bmmorp][Ac]has a strong physical affinity for H_(2)S and low energy requirement for desorption.Quantum chemical methods were used to investigate the molecular mechanism of H_(2)S absorption in ionic liquids.The interaction energy analysis revealed that the binding of H_(2)S with the ionic liquid in a1:2 ratio is more stable.Detailed analyses by the methods of the interaction region indicator and the atoms in molecules were conducted to the interactions between H_(2)S and the ionic liquid.

Synergy of inside doped metals–Outside coated graphene to enhance hydrogen storage in magnesium-based alloys

Grain growth of magnesium(Mg)and its hydride is one of the main reasons for kinetic and capacity degradation during the hydrogen absorption and desorption cycles.To solve this problem,herein we propose a novel method involving synergistic effect of inside embedded metals and outside coated graphene to limit the growth of Mg and its hydride grains.The graphene coated Mg-Y-Al alloys were selected as a model system for demonstrating this positive effect where the Mg_(91)Y_(3)Al_(6)alloy was first prepared by rapidly solidified method and then high-pressure milled with 5 wt%graphene upon 5 MPa hydrogen gas for obtaining in-situ formed YAl_(2)and YH_(3)embedded in the MgH_(2)matrix with graphene shell(denoted as MgH_(2)-Y-Al@GR).In comparison to pure MgH_(2),the obtained MgH_(2)-Y-Al@GR composites deliver much better kinetics and more stable cyclic performance.For instance,the MgH_(2)-Y-Al@GR can release about 6.1 wt%H_(2)within 30 min at 300℃ but pure MgH_(2)only desorbs∼1.5 wt%H_(2).The activation energy for desorption of MgH_(2)-Y-Al@GR samples is calculated to be 75.3±9.1 kJ/mol that is much lower than approximately 160 kJ/mol for pure MgH_(2).Moreover,its capacity retention is promoted from∼57%of pure MgH_(2)to∼84%after 50th cycles without obvious particle agglomeration and grain growth.The synergistic effect of outside graphene coating with inside embedded metals which could provide a huge number of active sites for catalysis as well as inhibit the grain growth of Mg and its hydride is believed to be responsible for these.

NH_(4)Cl-assisted synthesis of TaON nanoparticle applied to photocatalytic hydrogen and oxygen evolution from water

Oxynitride semiconductors are promising photocatalyst materials for visible light-driven water splitting,while the synthesis of well crystalized oxynitride still remains challenge.In present work,narrow-bandgap TaON nanoparticles are synthesized via heating a vacuum-sealed mixture of KTaO_(3),Ta and NH_(4)Cl.This method possesses multiple advantages in terms of lower calcination parameter,higher N conversion efficiency and superior photocatalytic activity in comparison with the traditional thermal ammonolysis using NH_(3) gas as a nitrogen source.Through the analysis of intermediates produced upon the elevation of heating temperature,a gas-solid-phase reaction between TaCl_(5) and Ta_(2)O_(5) is demonstrated as the final step,which is conducive to decreasing thermal energy barrier and accelerating nitridation process.Precise control of preparation conditions,including calcination temperature and duration,allows for the regulation of surface O/N ratio of TaON particles to unity,resulting in optimized photocat-alytic activity.Photoelectrochemical assessment and intensity modulated photocurrent spectroscopy provide convincing evidence for improved charge transfer effciency of photoexcited holes at TaON surface.A Z-scheme overall water splitting is accomplished by employing the TaON as an effective oxygen evolution photocatalyst,SrTiO_(3):Rh as a hydrogen evolution photocatalyst,and reduced graphene oxide(rGO)as a solid-state electron mediator.This work presents a promising strategy for the synthesis of high-quality oxynitride materials in application to photocatalytic water splitting.

Modification of BCC phase and the enhanced reversible hydrogen storage properties of Ti-V-Fe-Mn alloys with varied V/Fe ratios

Ti-V-based alloys are proved of huge potential in storing hydrogen,but the incomplete reversible hydrogen storage capacity caused by overstability of V hydride has limited the large-scale application.In this study,Ti_(32)V_(40+x)Fe_(23-x)Mn_(5)(x=0,4,8,12,at.%)alloys were designed,and the effects of V/Fe ratio on phase constitution and hydrogen storage properties were investigated.The main phase of the alloys is body-centered cubic(BCC)phase,and the lattice constants of the BCC phase decrease with the decrease of V/Fe ratio.Moreover,C14 Laves phase exists in alloys with a Fe content of 19at.%to 23at.%.For hydrogenation,the C14 Laves phase can accelerate the hydrogen absorption rate,but the hydrogen absorption capacity is reduced.With the decrease of V/Fe ratio,the hydride gradually destabilizes.Owing to its large lattice constant and high hydrogen absorption phase content,the Ti_(32)V_(52)Fe_(11)Mn_(5)alloy shows the most enhanced hydrogen storage properties with hydrogenation and dehydrogenation capacities of 3.588wt.%at 298 K and 1.688wt.%at 343 K,respectively.The hydrogen absorption capacity of this alloy can be reserved to 3.574wt.%after 20 cycles of hydrogen absorption and desorption.

Effect of Different Morphologies Induced by Solvent on ZIF-67 Derived Co@NC for Catalytic Phenol Hydrogenation

The Co@NC catalysts with different morphologies were prepared by two step process,solvent control growth and pyrolysis method.The polyhedral Co@NC-67P-450 catalyst has a relatively high CoNx content and exhibits excellent phenol hydrogenation activity(conversion 96.9%)at 160℃,3 MPa,which is higher than that of leaf shaped Co@NC-67L-450 catalyst(conversion 75.4%).We demonstrated Co_(3)O_(4)was reduced to the Co^(0)during the reaction.Moreover,CoNx species contribute to the superior hydrogenation activity of phenol.The Co-based catalysts can be easily recovered through the magnetic separation and performed the high stability.

Optimizing extractants selection for efficient separation of phenols and nitrogen-containing heteroaromatics using hydrogen bond interaction strategies

Focusing on the use of imidazolium ionic liquids and quaternary ammonium salts-based deep eutectic solvents for the separation of phenols and nitrogen-containing heteroaromatics,the role of heteroaromatics as specific sites for hydrogen bond-based separation has been investigated.These environmentally friendly solvents are known for their ability to form hydrogen bonds with heteroatoms,a key aspect in separation processes.We quantified the hydrogen bond interaction energy to reach the threshold energy for efficient O-and N-heteroaromatics separation.This article provides an in-depth study of the structural nuances of different hydrogen bonding sites and their affinity properties while conducting a comparative evaluation of the separation efficiency of ionic liquids and deep eutectic solvents from a thermodynamic perspective.Results showed that phenols with dual hydrogen bonding recognition sites were easier to separate than nitrogen-containing heteroaromatics.Imidazolium ionic liquids were more suitable for the extraction of nonbasic nitrogen-containing heteroaromatics,and quaternary ammonium salts-based deep eutectic solvents are more effective for phenols and basic nitrogen-containing heteroaromatics,which was confirmed by Fourier transform infrared spectroscopy and empirical tests.Therefore,this study provides a theoretical basis for the strategy design and selection of extractants for the efficient separation of O-and N-containing aromatic compounds.

Amorphous Iridium Oxide-Integrated Anode Electrodes with Ultrahigh Material Utilization for Hydrogen Production at Industrial Current Densities

Herein,ionomer-free amorphous iridium oxide(IrO_(x))thin electrodes are first developed as highly active anodes for proton exchange membrane electrolyzer cells(PEMECs)via low-cost,environmentally friendly,and easily scalable electrodeposition at room temperature.Combined with a Nafion 117 membrane,the IrO_(x)-integrated electrode with an ultralow loading of 0.075 mg cm^(-2)delivers a high cell efficiency of about 90%,achieving more than 96%catalyst savings and 42-fold higher catalyst utilization compared to commercial catalyst-coated membrane(2 mg cm^(-2)).Additionally,the IrO_(x)electrode demonstrates superior performance,higher catalyst utilization and significantly simplified fabrication with easy scalability compared with the most previously reported anodes.Notably,the remarkable performance could be mainly due to the amorphous phase property,sufficient Ir^(3+)content,and rich surface hydroxide groups in catalysts.Overall,due to the high activity,high cell efficiency,an economical,greatly simplified and easily scalable fabrication process,and ultrahigh material utilization,the IrO_(x)electrode shows great potential to be applied in industry and accelerates the commercialization of PEMECs and renewable energy evolution.

Enhanced reversible hydrogen storage properties of wrinkled graphene microflowers confined LiBH_(4) system with high volumetric hydrogen storage capacity

LiBH_(4)with high hydrogen storage density,is regarded as one of the most promising hydrogen storage materials.Nevertheless,it suffers from high dehydrogenation temperature and poor reversibility for practical use.Nanoconfinement is effective in achieving low dehydrogenation temperature and favorable reversibility.Besides,graphene can serve as supporting materials for LiBH_(4)catalysts and also destabilize LiBH_(4)via interfacial reaction.However,graphene has never been used alone as a frame material for nanoconfining LiBH_(4).In this study,graphene microflowers with large pore volumes were prepared and used as nanoconfinement framework material for LiBH_(4),and the nanoconfinement effect of graphene was revealed.After loading 70 wt%of LiBH_(4) and mechanically compressed at 350 MPa,8.0 wt% of H2 can be released within 100 min at 320C,corresponding to the highest volumetric hydrogen storage density of 94.9 g H2 L^(-1)ever reported.Thanks to the nanoconfinement of graphene,the rate-limiting step of dehydrogenation of nanoconfined LiBH_(4) was changed and its apparent activation energy of the dehydrogenation(107.3 kJ mol^(-1))was 42%lower than that of pure LiBH_(4).Moreover,the formation of the intermediate Li_(2)B_(12)H_(12) was effectively inhibited,and the stable nanoconfined structure enhanced the reversibility of LiBH_(4).This work widens the understanding of graphene's nanoconfinement effect and provides new insights for developing high-density hydrogen storage materials.

Hollow Ni Mo-based nitride heterojunction with super-hydrophilic/aerophobic surface for efficient urea-assisted hydrogen production

Hydrogen evolution reaction(HER)and urea oxidation reaction(UOR)are key reactions of the watercycling associated catalytic process/device.The design of catalysts with a super-hydrophilic/aerophobic structure and optimized electron distribution holds great promise.Here,we have designed a threedimensional(3D)hollow Ni/NiMoN hierarchical structure with arrayed-sheet surface based on a onepot hydrothermal route for efficient urea-assisted HER based on a simple hydrothermal process.The Ni/NiMoN catalyst exhibits super-hydrophilic/aerophobic properties with a small droplet contact angle of 6.07°and an underwater bubble contact angle of 155.7°,thus facilitating an escape of bubbles from the electrodes.Density functional theory calculations and X-ray photoelectron spectroscopy results indicate the optimized electronic structure at the interface of Ni and NiMoN,which can promote the adsorption/desorption of reactants and intermediates.The virtues combining with a large specific surface area endow Ni/NiMoN with efficient catalytic activity of low potentials of 25 mV for HER and 1.33 V for UOR at10 mA cm^(-2).The coupled HER and UOR system demonstrates a low cell voltage of 1.42 V at 10 mA cm^(-2),which is approximately 209 mV lower than water electrolysis.

Marrying luminescent metal nanoclusters to C_(3)N_(4) for efficient photocatalytic hydrogen peroxide production

Photocatalytic oxygen(O_(2))reduction has been considered a promising method for hydrogen peroxide(H_(2)O_(2))production.However,the poor visible light harvesting and low-efficient separation and generation of charge carriers of conventional photocatalysts strongly limited their photocatalytic H_(2)O_(2) generation performance.Herein,we design a highly efficient photocatalyst in this work by marrying luminescent gold-silver nanoclusters(AuAg NCs)to polyethyleneimine(PEI)modified C_(3)N_(4)(C3N4-PEI).The key design in this work is the utilization of highly luminescent AuAg NCs as photosensitizers to promote the generation and separation of charge carriers of C_(3)N_(4)-PEI,thereby ultimately producing abundant e−for O_(2) reduction under visible light illumination(λ≥400 nm).As a result,the as-designed photocatalyst(C3N4-PEI-AuAg NCs)exhibits excellent photocatalytic activity with an H_(2)O_(2) production capability of 82μM in pure water,which is 3.5 times higher than pristine C_(3)N_(4)(23μM).This interesting design provides a paradigm in developing other high-efficient photocatalysts for visible-light-driven H_(2)O_(2) production.

Graphene-loaded nickel−vanadium bimetal oxides as hydrogen pumps to boost solid-state hydrogen storage kinetic performance of magnesium hydride

To modify the thermodynamics and kinetic performance of magnesium hydride(MgH_(2))for solid-state hydrogen storage,Ni_(3)V_(2)O_(8)-rGO(rGO represents reduced graphene oxide)and Ni_(3)V_(2)O_(8)nanocomposites were prepared by hydrothermal and subsequent heat treatment.The beginning hydrogen desorption temperature of 7 wt.%Ni_(3)V_(2)O_(8)-rGO modified MgH_(2)was reduced to 208℃,while the additive-free MgH_(2)and 7 wt.%Ni_(3)V_(2)O_(8)doped MgH_(2)appeared to discharge hydrogen at 340 and 226℃,respectively.A charging capacity of about 4.7 wt.%H_(2)for MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO was achieved at 125℃ in 10 min,while the dehydrogenated MgH_(2)took 60 min to absorb only 4.6 wt.%H_(2)at 215℃.The microstructure analysis confirmed that the in-situ generated Mg_(2)Ni/Mg_(2)N_(i)H_(4) and metallic V contributed significantly to the enhanced performance of MgH_(2).In addition,the presence of rGO in the MgH_(2)+7 wt.%Ni_(3)V_(2)O_(8)-rGO composite reduced particle aggregation tendency of Mg/MgH_(2),leading to improving the cyclic stability of MgH_(2)during 20 cycles.

Enabling built-in electric fields on rhenium-vacancy-rich heterojunction interfaces of transition-metal dichalcogenides for pH-universal efficient hydrogen and electric energy generation

Most advanced hydrogen evolution reaction(HER)catalysts show high activity under alkaline conditions.However,the performance deteriorates at a natural and acidic pH,which is often problematic in practical applications.Herein,a rhenium(Re)sulfide–transition-metal dichalcogenide heterojunc-tion catalyst with Re-rich vacancies(NiS_(2)-ReS_(2)-V)has been constructed.The optimized catalyst shows extraordinary electrocatalytic HER performance over a wide range of pH,with ultralow overpotentials of 42,85,and 122 mV under alkaline,acidic,and neutral conditions,respectively.Moreover,the two-electrode system with NiS_(2)-ReS_(2)-V1 as the cathode provides a voltage of 1.73 V at 500 mA cm^(-2),superior to industrial systems.Besides,the open-circuit voltage of a single Zn–H_(2)O cell with NiS_(2)-ReS_(2)-V1 as the cathode can reach an impressive 90.9% of the theoretical value,with a maximum power density of up to 31.6 mW cm^(-2).Moreover,it shows remarkable stability,with sustained discharge for approximately 120 h at 10 mA cm^(-2),significantly outperforming commercial Pt/C catalysts under the same conditions in all aspects.A series of systematic characterizations and theoretical calculations demonstrate that Re vacancies on the heterojunction interface would generate a stronger built-in electric field,which profoundly affects surface charge distribution and subsequently enhances HER performance.

Pt nanoclusters modified porous g-C_(3)N_(4)nanosheets to significantly enhance hydrogen production by photocatalytic water reforming of methanol

For the use of green hydrogen energy,it is crucial to have efficient photocatalytic activity for hydrogen generation by water reforming of methanol under mild conditions.Much attention has been paid to gC_(3)N_(4)as a promising photocatalyst for the generation of hydrogen.To improve the separation of photogenerated charge,porous nanosheet g-C_(3)N_(4)was modified with Pt nanoclusters(Pt/g-C_(3)N_(4))through impregnation and following photo-induced reduction.This catalyst showed excellent photocatalytic activity of water reforming of methanol fo r hydrogen production with a 17.12 mmol·g^(-1)·h^(-1)rate at room temperature,which was 311 times higher than that of the unmodified g-C_(3)N_(4).The strong interactions of Pt-N in Pt/g-C_(3)N_(4)constructed effective electron transfer channels to promote the separation of photogenerated electrons and holes effectively.In addition,in-situ infrared spectroscopy was used to investigate the intermediates of the hydrogen production reaction,which proved that methanol and water eventually turn into H_(2)and CO_(2)via formaldehyde and formate.This study provides insights for understanding the photocatalytic hydrogen production in the water reforming of methanol.

Research on Scheduling Strategy of Flexible Interconnection Distribution Network Considering Distributed Photovoltaic and Hydrogen Energy Storage

Distributed photovoltaic(PV)is one of the important power sources for building a new power system with new energy as the main body.The rapid development of distributed PV has brought new challenges to the operation of distribution networks.In order to improve the absorption ability of large-scale distributed PV access to the distribution network,the AC/DC hybrid distribution network is constructed based on flexible interconnection technology,and a coordinated scheduling strategy model of hydrogen energy storage(HS)and distributed PV is established.Firstly,the mathematical model of distributed PV and HS system is established,and a comprehensive energy storage system combining seasonal hydrogen energy storage(SHS)and battery(BT)is proposed.Then,a flexible interconnected distribution network scheduling optimization model is established to minimize the total active power loss,voltage deviation and system operating cost.Finally,simulation analysis is carried out on the improved IEEE33 node,the NSGA-II algorithm is used to solve specific examples,and the optimal scheduling results of the comprehensive economy and power quality of the distribution network are obtained.Compared with the method that does not consider HS and flexible interconnection technology,the network loss and voltage deviation of this method are lower,and the total system cost can be reduced by 3.55%,which verifies the effectiveness of the proposed method.

Solar Driven 15.7% Hydrogen Conversion by Harmony of Light Harvesting,Electron Transporting Bridge,and S-Defection in a Self-Assembled Microscale CuS/rGO/CP Photoanode

CuS is an encouraging photoelectrode candidate that meets the essential requirements for efficient solar-to-hydrogen production,but it has not been thoroughly studied.A CuS light absorber layer is grown by the self-assembly of copper and sulfur precursors on a carbon paper(CP)electrode.Simultaneously,rGO is introduced as a buffer layer to control the optical and electrical properties of the absorber.The well-ordered microstructural arrangement suppresses the recombination loss of electrons and holes owing to enhanced charge-carrier generation,separation,and transport.The potential reaching 10 mA cm^(-2)in 1.0 M KOH solution is significantly lowered to 0.87 V,and the photocurrent density at 1.23 V is 94.7 mA cm^(-2).The computational result reveals that the potential-determining step is sensitive to O^(*)stability;the lower stability of O^(*)in the thin layer of CuS/rGO decreases the free-energy gap between the initial and final states of the potential-determining step,resulting in a lowering of the onset potential.The faradaic efficiency for the photoelectrochemical oxygen evolution reaction in the optimized 2CuS/1rGO/CP photoanode is 98.60%,and the applied bias photon-to-current and the solar-to-hydrogen efficiencies are 11.2%and 15.7%,respectively,and its ultra-high performance is maintained for 250 h.These record-breaking achievement indices may be a trigger for establishing a green hydrogen economy.

Strong hetero-interface interaction in 2D/2D WSe_(2)/ZnIn_(2)S_(4) heterostructures for highly-efficient photocatalytic hydrogen generation

Green hydrogen is urgently required for sustainable development of human beings and rational construction of heterostructures holds great promising for photocatalytic hydrogen generation.Herein,2D/2D WSe_(2)/ZnIn_(2)S_(4) heterostructures with strong hetero-interface interaction and abundant contact were constructed via an impregnation-annealing strategy.Efficient charge transfer from ZnIn_(2)S_(4) to WSe_(2)was evidenced by transient absorption spectroscopy in crafted heterostructures owing to the tight and2D face-to-face contact.As a result,the prepared WSe_(2)/ZnIn_(2)S_(4) heterostructures exhibited boosted photocatalytic performance and a highest hydrogen evolution rate of 3.377 mmol/(g h)was achieved with an apparent quantum yield of 45.7%at 420 nm.The work not only provides new strategies to achieve efficient 2D/2D heterostructures but also paves the way for the development of green hydrogen in the future.