Chalcogen heteroatoms doped nickel-nitrogen-carbon single-atom catalysts with asymmetric coordination for efficient electrochemical CO_(2)reduction

The electronic configuration of central metal atoms in single-atom catalysts(SACs)is pivotal in electrochemical CO_(2)reduction reaction(eCO_(2)RR).Herein,chalcogen heteroatoms(e.g.,S,Se,and Te)were incorporated into the symmetric nickel-nitrogen-carbon(Ni-N4-C)configuration to obtain Ni-X-N3-C(X:S,Se,and Te)SACs with asymmetric coordination presented for central Ni atoms.Among these obtained Ni-X-N3-C(X:S,Se,and Te)SACs,Ni-Se-N3-C exhibited superior eCO_(2)RR activity,with CO selectivity reaching~98%at-0.70 V versus reversible hydrogen electrode(RHE).The Zn-CO_(2)battery integrated with Ni-Se-N3-C as cathode and Zn foil as anode achieved a peak power density of 1.82 mW cm-2 and maintained remarkable rechargeable stability over 20 h.In-situ spectral investigations and theoretical calculations demonstrated that the chalcogen heteroatoms doped into the Ni-N4-C configuration would break coordination symmetry and trigger charge redistribution,and then regulate the intermediate behaviors and thermodynamic reaction pathways for eCO_(2)RR.Especially,for Ni-Se-N3-C,the introduced Se atoms could significantly raise the d-band center of central Ni atoms and thus remarkably lower the energy barrier for the rate-determining step of*COOH formation,contributing to the promising eCO_(2)RR performance for high selectivity CO production by competing with hydrogen evolution reaction.

Sequential Growth of Cs_(3)Bi_(2)I_(9)/BiVO_(4)Direct Z-Scheme Heterojunction for Visible-Light-Driven Photocatalytic CO_(2)Reduction

The high exciton binding energy and lack of a positive oxidation band potential restrict the photocatalytic CO_(2)reduction efficiency of lead-free Bi-based halide perovskites Cs_(3)Bi_(2)X_(9)(X=Br,I).In this study,a sequential growth method is presented to prepare a visible-light-driven(λ>420 nm)Z-scheme heterojunction photocatalyst composed of BiVO_(4)nanocrystals decorated on a Cs_(3)Bi_(2)I_(9)nanosheet for photocatalytic CO_(2)reduction coupled with water oxidation.The Cs_(3)Bi_(2)I_(9)/BiVO_(4)Z-scheme heterojunction photocatalyst is stable in the gas-solid photocatalytic CO_(2)reduction system,demonstrating a high visible-light-driven photocatalytic CO_(2)-to-CO production rate of 17.5μmol/(g·h),which is approximately three times that of pristine Cs_(3)Bi_(2)I_(9).The high efficiency of the Cs_(3)Bi_(2)I_(9)/BiVO_(4)heterojunction was attributed to the improved charge separation in Cs_(3)Bi_(2)I_(9).Moreover,the Z-scheme charge-transfer pathway preserves the negative reduction potential of Cs_(3)Bi_(2)I_(9)and the positive oxidation potential of BiVO_()4.This study off ers solid evidence of constructing Z-scheme heterojunctions to improve the photocatalytic performance of lead-free halide perovskites and would inspire more ideas for developing leadfree halide perovskite photocatalysts.

Electron-Deficient Zn-N_(6) Configuration Enabling Polymeric Carbon Nitride for Visible-Light Photocatalytic Overall Water Splitting

Despite of suitable band structures for harvesting solar light and driving water redox reactions,polymeric carbon nitride(PCN)has suffered from poor charge transfer ability and sluggish surface reaction kinetics,which limit its photocatalytic activity for water splitting.Herein,atomically dispersed Zn-coordinated three-dimensional(3D)sponge-like PCN(Zn-PCN)is synthesized through a novel intermediate coordination strategy.Advanced characterizations and theoretical calculations well evidence that Zn single atoms are coordinated and stabilized on PCN in the form of Zn-N_(6) configura-tion featured with an electron-deficient state.Such an electronic configuration has been demonstrated contributive to promoted electron excitation,accelerated charge separation and transfer as well as reduced water redox barriers.Further benefited from the abundant surface active sites derived from the 3D porous structure,Zn-PCN realizes visible-light photocatalysis for overall water splitting with H_(2) and O_(2) simultaneously evolved at a stoichiometric ratio of 2:1.This work brings new insights into the design of novel single-atom photocatalysts by deepening the understanding of electronic configurations and reactive sites favorable to excellent photocatalysis for water splitting and related solar energy conversion reactions.

Ultrafine polycrystalline titania nanofibers for superior sodium storage

Sodium ion batteries have a huge potential for large-scale energy storage for the low cost and abundance of sodium resources. In this work, a novel structure of ultrafine polycrystalline TiO2 nanofibers is prepared on nickel foam/carbon cloth by a simple vapor deposition method. The as-prepared TiO2 nanofibers show excellent performance when used as anodes for sodium-ion batteries. Specifically, the TiO2 nanofibers@nickel foam electrode delivers a high reversible capacity of 263.2 m Ahg^-1 at 0.2 C and maintains a considerable capacity of 144.2 m Ahg^-1 at 10 C. The TiO2 nanofibers@carbon cloth electrode also shows excellent high-rate capability, sustaining a capacity of 148 m Ahg^-1 after 20 0 0 cycles at 10 C. It is believed that the novel nanofibrous structure increases the contact area with the electrolyte and greatly shortens the sodium ion diffusion distance, and meanwhile, the polycrystalline nature of nanofibers exposes more intercalation sites for sodium storage. Furthermore, the density functional theory calculations exhibit strong ionic interactions between the exposed TiO2(101) facets and sodium ions, leading to a preferable sodiation/desodiation process. The unique structural features endow the TiO2 nanofibers electrodes great advantages in rapid sodium storage with an outstanding high-rate capability.

Photocatalytic water oxidation over BiVO_4 with interface energetics engineered by Co and Ni-metallated dicyanamides

Photocatalytic water oxidation based on semiconductors usually suffers from poor charge transfer from the bulk to the interface,which is necessary for oxygen generation.Here,we construct a hybrid artificial photosynthesis system for photocatalytic water oxidation.The system consists of BiVO4as the light harvester,a transitional metal complex(M(dca)2,M=Co,Ni,dca:dicyanamide)as the water oxidation catalyst,and S2O82?as a sacrificial electron acceptor.The system exhibits enhanced oxygen evolution activity when M(dca)2is introduced.The BiVO4/Co(dca)2and Bi‐VO4/Ni(dca)2systems exhibit excellent oxygen evolution rates of508.1and297.7μmol/(h·g)compared to the pure BiVO4which shows a photocatalytic oxygen evolution rate of252.2μmol/(h·g)during6h of photocatalytic reaction.Co(dca)2is found to be more effective than Ni(dca)2as a water oxidation catalyst.The enhanced photocatalytic performance is ascribed to the M(dca)2‐engineered BiVO4/electrolyte interface energetics,and to the M(dca)2‐catalyzed surface water oxidation.These two factors lead to a decrease in the energy barrier for hole transfer from the bulk to the surface of BiVO4,which promotes the water oxidation kinetics.

Polyacrylate modified Cu electrode for selective electrochemical CO_(2) reduction towards multicarbon products

Highly selective production of value-added multicarbon(C^(2+))products via electrochemical CO_(2) reduction reaction(eCO_(2)RR)on polycrystalline copper(Cu)remains challenging.Herein,the facile surface modification using poly(α-ethyl cyanoacrylate)(PECA)is presented to greatly enhance the C^(2+)selectivity for eCO_(2)RR over polycrystalline Cu,with Faradaic efficiency(FE)towards C^(2+)products increased from30.1%for the Cu electrode to 72.6%for the obtained Cu-PECA electrode at-1.1 V vs.reversible hydrogen electrode(RHE).Given the well-determined FEs towards C^(2+)products,the partial current densities for C^(2+)production could be estimated to be-145.4 mA cm~(-2)for the Cu-PECA electrode at-0.9 V vs.RHE in a homemade flow cell.In-situ spectral characterizations and theoretical calculations reveal that PECA featured with electron-accepting-C≡N and-COOR groups decorated onto the Cu electrode could inhibit the adsorption of^(*)H intermediates and stabilize the^(*)CO intermediates,given the redistributed interfacial electron density and the raised energy level of d-band center(E_(d))of Cu active sites,thus facilitating the C-C coupling and then the C^(2+)selective production.This study is believed to be guidable to the modification of electrocatalysts and electrodes with polymers to steer the surface adsorption behaviors of reaction intermediates to realize practical eCO_(2)RR towards value-added C^(2+)products with high activity and selectivity.

Function-reversible facets enabling SrTiO_(3)nanocrystals for improved photocatalytic hydrogen evolution

It has been widely reported that,for faceted nanocrystals,the two adjacent facets with different band levels contribute to promoted charge separation,and provide active sites for photocatalytic reduction and oxidation reaction,respectively.In such cases,only one family of facets can be used for photocatalytic hydrogen evolution.Herein,by using SrTiO_(3)nanocrystals enclosed by{023}and{001}facets as a model photocatalyst,this paper proposed a strategy to achieve the full-facets-utilization of the nanocrystals for photocatalytic hydrogen via chemically depositing Pt nanoparticles on all facets.The photo-deposition experiment of CdS provided direct evidence to demonstrate that the{023}facets which were responsible for photooxidation reaction can be function-reversed for photocatalytic hydrogen evolution after depositing Pt nanoparticles,together with the{001}facets.Thus,the full-facets-utilization led to a much-improved activity for photocatalytic hydrogen,in contrast to those SrTiO_(3)nanocrystals with only{001}facets deposited by Pt nanoparticles via a photo-deposition method.

Photocatalytic water splitting on BiVO_(4):Balanced charge-carrier consumption and selective redox reaction

Surficial redox reactions play an essential role in photocatalytic water splitting,and are closely related to the surface properties of a specific photocatalyst.In this work,using monoclinic BiVO_(4)decahedral single crystals as a model photocatalyst,we report on the interrelationship between the photocatalytic activity and the surficial reaction sites for charge-carrier consumption.By controlled hydrothermal synthesis,the ratio of{010}to{110}facets on BiVO_(4),which respectively serve as reductive and oxidative sites,is carefully tailored.Our results show that superior photocatalytic water oxidation could be obtained on BiVO_(4)decahedrons with a medium ratio of reductive/oxidative sites and that efficient overall water splitting could be achieved via further modification of appropriate cocatalysts in Z-scheme system.The excellent photocatalytic performance is attributed to the accelerated selective redox reactions by realizing balanced charge-carrier consumption,which provides insightful guidance for prospering photocatalytic reactions in energy conversion.

Activating ZnO nanorod photoanodes in visible light by Cu ion implantation

Utilization of visible light is of crucial importance for exploiting efficient semiconductor catalysts for solar water splitting. In this study, an advanced ion implantation method was utilized to dope Cu ions into ZnO nanorod arrays for photoelectrochemical water splitting in visible light. X-ray diffraction （XRD） and X-ray photo-electron spectroscopy （XPS） results revealed that Cu^＋ together with a small amount of Cu^2＋ were highly dispersed within the ZnO nanorod arrays. The Cu ion doped ZnO nanorod arrays displayed extended optical absorption and enhanced photoelectrochemical performance under visible light illumination （A 〉 420 nm）. A considerable photocurrent density of 18 μA/cm^2 at 0.8 V （vs. a saturated calomel electrode） was achieved, which was about 11 times higher than that of undoped ZnO nanorod arrays. This study proposes that ion implantation could be an effective approach for developing novel visible-light-driven photocatalytic materials for water splitting.

Function-switchable metal/semiconductor junction enables efficient photocatalytic overall water splitting with selective water oxidation products

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)light.This Cu/TiO2 photocatalyst possesses excellent POWS performance under Vis light at the highest level among the reported TiO2-based photocatalysts.Interestingly,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 wavelengths.Under 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 process.This rational design of function-switchable metal/semiconductor junction may be helpful to understand the mechanisms for POWS with desired gas/liquid water-oxidation products.

Surface sulfurization activating hematite nanorods for efficient photoelectrochemical water splitting

Surface treatment is an effective method to improve the photoelectrochemical(PEC) performance of photoelectrodes. Herein, we introduced a novel strategy of surface sulfurization to modify hematite(a-Fe2 O3)nanorods grown in an aqueous solution, which triggered encouraging improvement in PEC performances.In comparison to the solution-grown pristine a-Fe2 O3 nanorod photoanode that is PEC inefficient and always needs high temperature(>600 °C) activation, the surface sulfurized a-Fe2 O3 nanorods show photocurrent density increased by orders of magnitude, reaching 0.46 mA cmà2 at 1.23 V vs. RHE(reversible hydrogen electrode) under simulated solar illumination. This improvement in PEC performances should be attributed to the synergy of the increased carrier density, the reduced surface charge carrier recombination and the accelerated water oxidation kinetics at the a-Fe2 O3/electrolyte interface, as induced by the incorporation of S ions and the formation of multi-state S species(Fe-Sx-Oy) at the surface of a-Fe2 O3 nanorods. This study paves a new and facile approach to activate a-Fe2 O3 and even other metal oxides as photoelectrodes for improved PEC water splitting performances, by engineering the surface structure to relieve the bottlenecks of charge transfer dynamics and redox reaction kinetics at the electrode/electrolyte interface.

Ferrites boosting photocatalytic hydrogen evolution over graphitic carbon nitride: a case study of(Co, Ni)Fe_2O_4 modification

The charge cartier separation and surface catalytic redox reactions are of primary importance as elementary steps in photocatalytic hydrogen evolution. In this study, both of these two processes in photocatalytic hydrogen evolution over graphitic carbon nitride （g-C3N4） were greatly promoted with the earth-abundant ferrites （Co, Ni）Fe2O4 modification. CoFe2O4 was further demonstrated to be a better modifier for g-C3N4 as compared to NiFe2O4, due to the more efficient charge carrier transfer as well as superior surface oxidative catalytic activity. When together loading CoFe2O4 and reductive hydrogen production electrocatalyst Pt onto g-C3N4, the obtained Pt/g-C3N4/CoFe2O4 photocatalyst achieved visible-light （2 〉 420 nm） hydrogen production rate 3.5 times as high as Pt/g-C3N4, with the apparent quantum yield reaching 3.35 % at 420 nm.

Au@SiO_2 core/shell nanoparticle-decorated TiO_2 nanorod arrays for enhanced photoelectrochemical water splitting

To improve the separation efficiency of photoinduced charge carries,Au@SiO2nanoparticles(NPs)with core–shell structure were loaded onto the surface of TiO2nanorods grown on fluorine-doped tin oxide substrate by a facile two-step process.The resulted Au@SiO2/TiO2photoanodes were characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,as well as photoelectrochemical measurements.Compared with pristine TiO2nanorod film,the Au@SiO2/TiO2films showed remarkable enhancement in photoelectrochemical water splitting,with incident photonto-current conversion efficiency increasing from 31%to37%at 380 nm at 0.7 V versus saturated calomel electrode.This could be interpreted by the effect of metallic surface plasmon resonance of Au@SiO2NPs,which would generate an intense electromagnetic field with spatially nonhomogenous distributed intensity.As a result,the charge carriers generated in the near-surface region of TiO2nanorods could be easily separated.This modification method based on the effect of metallic surface plasmon resonance for promoted charge carrier separation provides a promising way to develop semiconductor photoelectrodes with high solar water-splitting performance.

Homojunction photocatalysts for water splitting

Charge-carrier separation is regarded as one of the critical issues of photocatalytic water splitting and could be accelerated by constructing microscopic junctions in photocatalysts.Homojunction photocatalysts consisting of different forms of semiconductor with identical compositions could inherit the advantages of heterojunction-based photocatalysts in charge separation due to the built-in electric field,while omitting the potential drawbacks of interfacial lattice distortion by providing continuous band bonding.Therefore,homojunction-based photocatalysts have recently drawn growing attention in water splitting.In this review,the synthetic approaches to preparing photocatalysts with various homojunction structures including p-n junction,phase junction,and facet junction were introduced,together with a comprehensive analysis and discussion on the latest progress in the application of photocatalytic water splitting.This review work is expected to inspire more related work with promoted research on designing efficient homojunction-based photocatalytic systems for water splitting.

Black TiO_(2) for solar hydrogen conversion

Titanium dioxide(TiO_(2))has been widely investigated for photocatalytic H_(2) evolution and photoelectrochemical(PEC)water splitting since 1972.However,its wide bandgap(3.0-3.2 eV)limits the optical absorption of TiO_(2) for sufficient utilization of solar energy.Blackening TiO_(2) has been proposed as an effective strategy to enhance its solar absorption and thus the photocatalytic and PEC activities,and aroused widespread research interest.In this article,we reviewed the recent progress of black TiO_(2) for photocatalytic H_(2) evolution and PEC water splitting,along with detailed introduction to its unique structural features,optical property,charge carrier transfer property and related theoretical calculations.As summarized in this review article,black TiO_(2) could be a promising candidate for photoelectrocatalytic hydrogen generation via water splitting,and continuous efforts are deserved for improving its solar hydrogen efficiency.

Boosting photocatalytic hydrogen production by creating isotype heterojunctions and single-atom active sites in highly-crystallized carbon nitride

Carbon nitride-based photocatalysts hold an enormous potential in producing hydrogen.A strategy to simultaneously create isotype heterojunctions and active sites in highly-crystallized carbon nitride is anticipated to significantly boost the photocatalytic activity,but is yet to be realized.Herein,we find that cobalt salt added in the ionothermal synthesis can promote the phase transition of heptazine-based crystalline carbon nitride(CCN)to triazine-based poly(triazine imide)(PTI),rendering the creation of singleatom cobalt coordinated isotype CCN/PTI heterojunction.Co-CCN/PTI exhibits an appreciable apparent quantum yield of 20.88%at 425 nm for photocatalytic hydrogen production with a rate achieving3538μmol h^(-1)g^(-1)(λ>420 nm),which is 4.8 times that of CCN and 27.6 times that of PTI.The high photocatalytic activity is attributed to the Type II isotype highly-crystallized CCN/PTI heterojunction for promoting charge carrier migration,and the single-atom Co sites for accelerating surface oxidation reaction.

A n-Si/CoOx/Ni:CoOOH photoanode producing 600 mV photovoltage for efficient photoelectrochemical water splitting

n-Si,believed as a promising photoanode candidate,has suffered from sluggish oxygen evolution reaction(OER)kinetics and poor chemical stability when exposed to aqueous electrolyte.Herein,CoO_(x)/Ni:CoOOH bilayers were successfully deposited on n-Si substrate by atomic layer-deposition(ALD)and photoassisted electrochemical deposition(PED)for stabilizing and catalyzing photoelectrochemical(PEC)water oxidation.In comparison to the n-Si/CoO_(x)photoanode as reference,the prepared n-Si/CoO_(x)/Ni:CoOOH photoanode upon the optimized PED process presents a much improved PEC performance for water splitting,with the onset potential cathodically shifted to~1.03 V vs.reversible hydrogen electrode(RHE)and the photocurrent density much increased to 20 mA cm^(−2)at 1.23 V vs.RHE.It is revealed that the introduction of Ni dopants increases the work functions of the deposited Ni:CoOOH overlayers,which gives rise to the upward band bending weakened at the n-Si/CoO_(x)/Ni:CoOOH cascading interface while strengthened at the Ni:CoOOH/electrolyte interface(with the band bending shifted from downward to upward),contributing to the decreased and the increased driving forces for charge transfer at the interfaces,respectively.Then,the balanced driving forces at the interfaces would endow the n-Si/CoO_(x)/Ni:CoOOH photoanode with the best PEC performance.Moreover,PED has been evidenced superior to ED to dope Ni into CoOOH with the formed overlayer effectively catalyzing and stabilizing PEC water splitting.

CdS nanocrystallites sensitized ZnO nanorods with plasmon enhanced photoelectrochemical performance

A novel architecture of CdS/ZnO nanorods with plasmonic silver(Ag) nanoparticles deposited at the interface of ZnO nanorods and CdS nanocrystallites,was designed as a photoanode for solar hydrogen generation,with photocurrent density achieving 4.7 mA/cm^2 at 1.6 V(vs.RHE),which is 8 and 1.7 times as high as those of pure ZnO and CdS/ZnO nanorod films,respectively.Additionally,with optical absorption onset extended to^660 nm,CdS/Ag/ZnO nanorod film exhibits significantly increased incident photo-tocurrent efficiency(IPCE) in the whole optical absorption region,reaching 23.1% and 9.8% at 400 nm and500 nm,respectively.The PEC enhancement can be attributed to the one-dimensional ZnO nanorod structure maintained for superior charge transfer,and the extended visible-light absorption of CdS nanocrystallites.Moreover,the incorporated plasmonic Ag nanoparticles could further promote the interfacial charge carrier transfer process and enhance the optical absorption ability,due to its excellent plasmon resonance effect.

Regulation on polymerization degree and surface feature in graphitic carbon nitride towards efficient photocatalytic H2 evolution under visible-light irradiation

A kind of graphitic carbon nitride(TSC-550) with high polymerization degree and improved surface property was prepared by a new precursor of thiosemicarbazide. The sulfur motif and high nitrogen content in thiosemicarbazide promoted the polymerization of thiosemicarbazide to form graphitic carbon nitride framework with high degree of polymerization, which significantly influenced the electronic structure and surface chemical properties. TSC-550 possessed a narrow bandgap of 2.19 eV that facilitated the utilization of visible light, and possessed a less positive charge, acidic surface that resulted in enhanced hydrogen adsorption ability in water solution, which promoted the H;evolution kinetics. In addition, the extended π-conjugated electronic system promoted the separation and migration of photogenerated charge carries in plane of TSC-550 framework, as well as the increasing interlayer C–N interactions in TSC-550 created conductive paths across the layers to tunnel interlayers for rapid electron transportation. As a result, TSC-550 nanosheets showed excellent photocatalytic H;production activity,the AQY achieved 36.4% at 425 nm.

Manipulating metal-oxygen local atomic structures in singlejunctional p-Si/WO_(3) photocathodes for efficient solar hydrogen generation

Self-passivation in aqueous solution and sluggish surface reaction kinetics significantly limit the photoelectrochemical(PEC)performances of silicon-based photoelectrodes.Herein,a WO_(3) thin layer is deposited on the p-Si substrate by pulsed laser deposition(PLD),acting as a photocathode for PEC hydrogen generation.Compared to bare p-Si,the single-junctional p-Si/WO_(3) photoelectrodes exhibit excellent and stable PEC performances with significantly increased cathodic photocurrent density and exceptional anodic shift in onset potential for water reduction.It is revealed that the WO_(3) layer could reduce the charge transfer resistance across the electrode/electrolyte interface by eliminating the effect of Fermi level pinning on the surface of p-Si.More importantly,by varying the oxygen pressures during PLD,the collaborative modulation of W–O bond covalency and WO6 octahedral structure symmetry contributes to the promoted charge carrier transport and separation.Meanwhile,a large band bending at the p-Si/WO_(3) junction,induced by the optimized O vacancy contents in WO_(3),could provide a photovoltage as high as~500 mV to efficiently drive charge transfer to overcome the water reduction overpotential.Synergistically,by manipulating W–O local atomic structures in the deposited WO_(3) layer,a great improvement in PEC performance could be achieved over the singlejunctional p-Si/WO_(3) photocathodes for solar hydrogen generation.