Artificial photosynthesis presents a sustainable and cost-effective approach to harnessing solar energy to produce value-added chemicals[1,2].In particular,the simultaneous photocatalytic conversion of CO_(2)and H_(2)...Artificial photosynthesis presents a sustainable and cost-effective approach to harnessing solar energy to produce value-added chemicals[1,2].In particular,the simultaneous photocatalytic conversion of CO_(2)and H_(2)O into formic acid(HCOOH)and hydrogen peroxide(H2O2)has emerged as a promising strategy to mitigate global warming driven by CO_(2)emissions.HCOOH is a versatile chemical and hydrogen carrier,offering economic and practical advantages due to its compatibility with existing industrial processes and energy storage/conversion systems.Meanwhile,H_(2)O_(2)is among the world’s top 100 essential chemicals,with a global market valued at$4.0 billion in 2020 and projected to grow to$5.2 billion by 2026.展开更多
Severe polysulfide shuttling and sluggish sulfur redox kinetics significantly decrease sulfur utilization and cycling stability in lithium-sulfur batteries(LSBs).Herein,we develop a hollow CoO/CoP-Box core-shell heter...Severe polysulfide shuttling and sluggish sulfur redox kinetics significantly decrease sulfur utilization and cycling stability in lithium-sulfur batteries(LSBs).Herein,we develop a hollow CoO/CoP-Box core-shell heterostructure as a model and multifunctional catalyst modified on separators to induce interfacial charge modulation and expose more active sites for promoting the adsorption and catalytic conversion ability of sulfur species.Theoretical and experimental findings verify that the in-situ formed core-shell hetero-interface induces the formation of P-Co-O binding and charge redistribution to activate surface O active sites for binding lithium polysulfides(LiPSs)via strong Li-O bonding,thus strongly adsorbing with Li PSs.Meanwhile,the strong Li-O bonding weakens the competing Li-S bonding in LiPSs or Li2S adsorbed on CoO/CoP-Box surface,plus the hollow heterostructure provides abundant active sites and fast electron/Li+transfer,so reducing Li2S nucleation/dissolution activation energy.As expected,LSBs with CoO/CoP-Box modified separator and traditional sulfur/carbon black cathode display a large initial capacity of 1240 mA h g^(-1)and a long cycling stability with 300 cycles(~60.1%capacity retention)at 0.5C.Impressively,the thick sulfur cathode(sulfur loading:5.2 mg cm^(-2))displays a high initial areal capacity of 6.9 mA h cm^(-2).This work verifies a deep mechanism understanding and an effective strategy to induce interfacial charge modulation and enhance active sites for designing efficient dual-directional Li-S catalysts via engineering hollow core-shell hetero-structure.展开更多
The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,wh...The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,while the challenge associated with N_(2) activation highlights the demand for efficient electrocatalysts.Herein,we demonstrate that PdCu nanoparticles with different Pd/Cu ratios anchored on boron nanosheet(PdCu/B)behave as efficient NRR electrocatalysts toward NH_(3) synthesis.Theoretical and experimental results confirm that the highly efficient NH_(3) synthesis can be achieved by regulating the charge transfer between interfaces and forming a symmetry-breaking site,which not only alleviates the hydrogen evolution but also changes the adsorption configuration of N_(2) and thus optimizes the reaction pathway of NRR over the separated Pd sites.Compared with monometallic Pd/B and Cu/B,the PdCu/B with the optimized Pd/Cu ratio of 1 exhibits superior activity and selectivity for NH_(3) synthesis.This study provides new insight into developing efficient catalysts for small energy molecule catalytic conversion via regulating the charge transfer between interfaces and constructing symmetry-breaking sites.展开更多
It is crucial to efficiently separate and transport photo-induced charge carriers for the effective implementation of photocatalysis toward environmental remediation.A rational design strategy is proposed to validate ...It is crucial to efficiently separate and transport photo-induced charge carriers for the effective implementation of photocatalysis toward environmental remediation.A rational design strategy is proposed to validate such proposition through the construction of an interfacial structure in the form of LDH/Zn_(2)SnO_(4) heterostructures in this research.The interfacial charge transfer on LDH/Zn_(2)SnO_(4) is greatly promoted via the unique charge transfer pathway,as characterized by transient photocurrent responses,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectrum,and photoluminescence analysis.As such,it contributes to the generation of reactive oxygen species(ROS)and the activation of reactants for the mineralization of toluene.According to the in situ DRIFTS spectra analysis,the accumulation of benzoic acid takes place possibly through the partial oxidation of the methyl group on toluene at the interface of the LDH/Zn 2 SnO 4 heterostructure.This process can greatly promote the photocatalytic oxidation of toluene with the enhanced ring-opening efficiency.The LDH/Zn 2 SnO 4 is thus demonstrated as superior photocatalyst against toluene(removal efficiency of 89.5%;mineralization of 83.1%;and quantum efficiency of 4.55×10^(−6) molecules/photon).As such,the performance of this composite far exceeds that of their individual components(e.g.,P25,pure Mg-Al LDH,or Zn_(2)SnO_(4)).This study is expected to offer a new path to the interfacial charge transfer mechanism based on the design of highly efficient photocatalysts for air purification.展开更多
The charge carrier separation efficiency and the adsorption capacity of the photocatalyst usually affect the degradation rate of antibiotics.Herein,Cerium-doped leaf-like CdS(Ce-CdS)modified with ultrathin N-doped rGO...The charge carrier separation efficiency and the adsorption capacity of the photocatalyst usually affect the degradation rate of antibiotics.Herein,Cerium-doped leaf-like CdS(Ce-CdS)modified with ultrathin N-doped rGO(N-rGO)composites were successfully constructed(Ce-CdS/N-rGO)to investigate the removal efficiency of tetracycline(TC).X-ray photoelectron spectroscopy(XPS)and photoelectrochemical results revealed that Ce ions doped in CdS acting as the electron capture sites facilitated the interfacial charge transfer.Theoretical calculation(DFT)results indicated that the interfacial effect between Ce-CdS and ultrathin N-rGO promoted the transfer of photogenerated electrons under the synergistic effect between the doping and interface modification strategy.The optimized Ce5-CdS/N-rGO20 composites had the maximum TC removal capability(94.5%)and maintained a stable cycling performance.In addition,the adsorption-driven photocatalytic degradation pathway of TC was studied through mass spectrometry(MS)and in-situ Fourier transform infrared spectroscopy(in-situ FTIR).This study will provide an effective strategy for the construction of efficient photocatalytic composites for wastewater treatment.展开更多
Pb-free Sn-based perovskite solar cells(PSCs) have recently made inspiring progress, and power conversion efficiency(PCE) of 14.8% has been achieved. However, due to the energy-level mismatch and poor interfacial cont...Pb-free Sn-based perovskite solar cells(PSCs) have recently made inspiring progress, and power conversion efficiency(PCE) of 14.8% has been achieved. However, due to the energy-level mismatch and poor interfacial contact between commonly used hole transport layer(i.e., poly(3,4-ethylenedioxythio phene):poly(styrene sulfonate), PEDOT:PSS) and FASnI_(3) film, it is still challenging to effectively extract holes at the interface. Owing to the p-type nature of Sn-based perovskites, the efficient hole extraction is of particular significance to improve the PCE of their solar cells. In this work, for the first time, the role of chiral cations, a-methylbenzylamine(S-/R-/rac-MBA), in promoting hole transportation of FASnI_(3)-based PSCs is demonstrated. The introduction of MBAs is found to form 2D/3D film with lowdimensional structures locating at PEDOT:PSS/FASnI_(3) interface, which facilitates the energy level alignment and efficient charge transfer at the interface. Importantly, chiral-induced spin selectivity(CISS)effect of R-MBA_(2)SnI_(4)induced by chiral R-MBA cation is found to further assist the specific interfacial transport of accumulated holes. As a result, R-MBA-based PSCs achieve decent PCE of 10.73% with much suppressed hysteresis and enhanced device stability. This work opens up a new strategy to efficiently promote the interfacial extraction of accumulated charges in working PSCs.展开更多
Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy,the challenging charge separation process and sluggish surface catalytic reactions significantly limit p...Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy,the challenging charge separation process and sluggish surface catalytic reactions significantly limit progress in solar energy conversion using semiconductor photocatalysts.Herein,we demonstrate a feasible strategy involving the surface assembly of cobalt oxide species(CoO_(x))on a visible-light-responsive Cd_(0.9)Zn_(0.1)S(CZS)photocatalyst to fabricate a hierarchical CZS@CoO_(x) heterostructure.The unique hierarchical structure effectively accelerates the directional transfer of photogenerated charges,reducing charge recombination through the smooth interfacial heterojunction between CZS and CoO_(x),as evidenced by photoluminescence(PL)spectroscopy and various electrochemical characterizations.The surface cobalt species on the CZS material also act as efficient cocatalysts for photocatalytic hydrogen production,with activity even higher than that of noble metals.The well-defined CZS@CoO_(x) heterostructure not only enhances the interfacial separation of photoinduced charges,but also improves surface catalytic reactions.This leads to superior photocatalytic performances,with an apparent quantum efficiency of 20%at 420 nm for visible-light-driven hydrogen generation,which is one of the highest quantum efficiencies measured among noble-metal-free photocatalysts.Our work presents a potential pathway for controlling complex charge separation and catalytic reaction processes in photocatalysis,guiding the practical development of artificial photocatalysts for successful transformation of solar to chemical energy.展开更多
The modulation of electrical properties of MoS_2 has attracted extensive research interest because of its potential applications in electronic and optoelectronic devices.Herein,interfacial charge transfer induced elec...The modulation of electrical properties of MoS_2 has attracted extensive research interest because of its potential applications in electronic and optoelectronic devices.Herein,interfacial charge transfer induced electronic property tuning of MoS_2 are investigated by in situ ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy measurements.A downward band-bending of MoS_2-related electronic states along with the decreasing work function,which are induced by the electron transfer from Cs overlayers to MoS_2,is observed after the functionalization of MoS_2 with Cs,leading to n-type doping.Meanwhile,when MoS_2 is modified with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane(F_4-TCNQ),an upward band-bending of MoS_2-related electronic states along with the increasing work function is observed at the interfaces.This is attributed to the electron depletion within MoS_2 due to the strong electron withdrawing property of F_4-TCNQ,indicating p-type doping of MoS_2.Our findings reveal that surface transfer doping is an effective approach for electronic property tuning of MoS_2 and paves the way to optimize its performance in electronic and optoelectronic devices.展开更多
Bismuth vanadate(BiVO_(4))is a promising photoanode material for photoelectrochemical(PEC)water oxidation.However,its performance is greatly hindered by poor bulk and interfacial charge transfer.Herein,to address this...Bismuth vanadate(BiVO_(4))is a promising photoanode material for photoelectrochemical(PEC)water oxidation.However,its performance is greatly hindered by poor bulk and interfacial charge transfer.Herein,to address this issue,iron doped vanadyl phosphate(Fe:VOPO_(4))was grafted on molybdenum doped BiVO_(4)(Mo:BiVO_(4))for significantly enhancing charge transfer and oxygen evolution kinetics simultaneously.Consequently,the resultant Fe:VOPO_(4)/Mo:BVO_(4) photoanode exhibits a remarkable photocurrent density of 6.59 mA cm^(-2) at 1.23 V versus the reversible hydrogen electrode(VRHE)under AM 1.5G illumination,over approximately 5.5 times as high as that of pristine BiVO_(4).Systematic studies have demonstrated that the hopping activation energy of small polarons is significantly reduced due to the Mo doping,resulting in accelerated bulk charge transfer.More importantly,the deposition of Fe:VOPO_(4) promotes the interfacial charge transfer between Mo:BiVO_(4) and Fe:VOPO_(4) via the construction of V-O-V and P-O bonds,in addition to facilitating water splitting kinetics.This work provides a general strategy for optimizing charge transfer process,especially at the interface between photoanodes and cocatalysts.展开更多
In strongly correlated transition metal oxide(TMO)systems,the anomalous Hall effect(AHE)can not only reveal the underlying physical mechanism of the coupling between multiple degrees of freedom,but also generate spin ...In strongly correlated transition metal oxide(TMO)systems,the anomalous Hall effect(AHE)can not only reveal the underlying physical mechanism of the coupling between multiple degrees of freedom,but also generate spin current-driven magnetization switching.However,enhancing the AHE in this system remains a significant challenge at present.This work systematically investigates the electronic transport properties of SrIrO_(3)/NiCo_(2)O_(4)(SIO/NCO)heterostructures,showing that the AHE of SIO/NCO heterostructures is enhanced by an order of magnitude compared to the ferrimagnetic NCO single film.The enhancement of AHE is more significant as the thickness of the SIO sublayer decreases,which is attributed to the fact that large strain exacerbates the interfacial charge transfer.This is demonstrated through the variation of binding energies and concentrations of electronic states in the X-ray photoelectron spectroscopy.Moreover,the AHE in SIO/NCO heterostructures arises from the synergistic effect of the intrinsic mechanism dominated by Berry curvature and the extrinsic mechanism caused by impurity scattering.This finding paves the way for advancing the reliability of TMO-based spintronic devices.展开更多
Correction to:Nano-Micro Letters(2025)17:117 https://doi.org/10.1007/s40820-025-01660-0 Following publication of the original article[1],the authors reported that the supplementary file needed to be updated because th...Correction to:Nano-Micro Letters(2025)17:117 https://doi.org/10.1007/s40820-025-01660-0 Following publication of the original article[1],the authors reported that the supplementary file needed to be updated because they mistakenly used the incorrect version.The original article[1]has been corrected.展开更多
The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-ba...The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.展开更多
The impact of interfacial charge on catalytic performance of supported-metal-cluster(SMC)heterostructures remains unclear,hindering efforts to develop high-performance SMC catalysts.Herein we systematically investigat...The impact of interfacial charge on catalytic performance of supported-metal-cluster(SMC)heterostructures remains unclear,hindering efforts to develop high-performance SMC catalysts.Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters(AuNCs/rGO)for azo hydrogenation.Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol(CSH),amphoteric cysteine(Cys),and electronegative 3-mercaptopropionic-acid(MPA)onto AuNCs/rGO,respectively.All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes.The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO.However,the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO.Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH_(4) action,leading to reduced efficiency and cyclic stability.Conversely,non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration,resulting in better cyclic stability.Protection of amino groups in ligands such as modifying-NH_(3)^(+)group in Cys into imine to form N-isobutyryl-L-cysteine(NIBC)substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system.Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.展开更多
The interfacial characteristics of the Li metal anode(LMA)play a crucial role in its overall performance.Despite various materials being applied to modify the interface,a comprehensive understanding of their specific ...The interfacial characteristics of the Li metal anode(LMA)play a crucial role in its overall performance.Despite various materials being applied to modify the interface,a comprehensive understanding of their specific mechanisms remains to be investigated.Herein,we have prepared carbon cloth(CC)frameworks with their surfaces modified using ferromagnetic metal/LiF heterogeneous films(T^(M)-LiF-CC)as the substrate for LMA,which exhibit superior electrochemical performance.Utilizing ferromagnetic Co as a representative example,our study demonstrates that the enhanced performance of Co-LiF-CC,compared to bare CC,is attributed to the spinpolarized interface contributed by the Co/LiF heterostructure.Co and LiF play individual roles in redistributing electrons and Li^(+)to promote homogeneous Li deposition.Co nanoparticles play a crucial role in generating strong surface capacitance by storing electrons in spin-split bands,while LiF,with low surface diffusion barriers,ensures fast transportation of Li^(+).The Co-LiF-CC@Li electrodes deliver long lives of 7400 and 3600 h at 1 and 2 mA·cm^(-2)in symmetric cells,respectively;moreover,they enable full batteries with high and durable capacities,particularly when the N/P ratios are low(3.3 or even 1.7).展开更多
Atomically precise metal nanoclusters(NCs)have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties,discrete energy band structure,and quantum confinem...Atomically precise metal nanoclusters(NCs)have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties,discrete energy band structure,and quantum confinement effect,which are distinct from conventional metal nanoparticles(NPs).Nevertheless,metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs,markedly reducing the photosensitization of metal NCs.Herein,maneuvering the generic instability of metal NCs,we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical(PEC)water splitting reaction.For conceptual demonstration,we proposed two quintessential heterostructures,which include TNTAs-Au_(25)heterostructure fabricated by electrostatically depositing glutathione(GSH)-protected Au_(25)(GSH)_(18)NCs on the TiO_(2)nanotube arrays(TNTAs)substrate,and TNTAs-Au heterostructure constructed by triggering self-transformation of Au_(25)(GSH)_(18)NCs to plasmonic Au NPs in TNTAs-Au_(25)via calcination.The results indicate that photoelectrons produced over Au_(25)NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation.This is mainly ascribed to the significantly accelerated carrier transport kinetics,prolonged carrier lifespan,and substantial photosensitization effect of Au_(25)NCs compared with plasmonic Au NPs,resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au_(25)relative to plasmonic TNTAs-Au counterpart under visible light irradiation.Our work would provide important implications for rationally designing atomically precise metal NCsbased photosystems toward solar energy conversion.展开更多
The present paper covers the lipid-free rhodium tetrasulfonato-phthalocyanine (RhTSPc) films prepared on p-Si(111) by using Langmuir-Blodgett technique. Their surface photovoltage spectra were measured. It was found t...The present paper covers the lipid-free rhodium tetrasulfonato-phthalocyanine (RhTSPc) films prepared on p-Si(111) by using Langmuir-Blodgett technique. Their surface photovoltage spectra were measured. It was found that there is a strong interaction at the interface between the RhTSPc film and p-Si (111) and that the surface photovoltaic effect of the film system is maximum when only one monolayer of RhTSPc molecules coats p-Si(111), which is similar to that of CuTSPc films on p-Si(111) reported previously. These results confirm that only the monolayer of dye molecules being adjacent to the semiconductor surface plays a key role in the light-induced interfacial charge transfer process.展开更多
Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance...Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance efficiency of such devices,yet the underlying mecha-nism,especially the roles of optical-ly dark triplets and spatially sepa-rated charge transfer states,is poorly understood.In the present work,we obtain the struc-tures of distinct excited states and investigate how they are involved in the charge transfer process at the Pd-octaethylporphyrin(PdOEP)and WS_(2) interface in terms of their energies and couplings.The results show that electron transfer from the triplet PdOEP formed via intersystem crossing prevails over direct electron transfer from the singlet(two orders of magnitude faster).Further analysis reveals that the relatively higher rate of triplet electron transfer compared to singlet electron transfer is mainly attributed to a smaller reorganization energy,which is dominated by the out-of-plane vibrations of the organic component.The work emphasizes the important roles of the optically dark triplets in the electron transfer of the PdOEP@WS_(2) heterostructure,and provides valuable theoretical insights for further improv-ing the optoelectronic performance of TMD-based devices.展开更多
The photoelectrocatalytic(PEC)CO_(2)reduction process includes photogenerated charge transport,multiphase interface,intermediate adsorption,and chemical bonding transformation,all of which are closely associated with ...The photoelectrocatalytic(PEC)CO_(2)reduction process includes photogenerated charge transport,multiphase interface,intermediate adsorption,and chemical bonding transformation,all of which are closely associated with the interface and surface layer on the photocathode.However,it is difficult to design the photocathode with an effective interface and surface active site for realizing the highly selective PEC CO_(2)reduction at ultralow potential.Here,we design a novel semiconductor p-n junction comprising Si nanowires and an indium-edited porphyrin-based metal-organic framework{Al/In-PMOF(Co)}for efficient CO_(2)reduction.The Al/In-PMOF(Co)catalyst containing In and Co metal atoms demonstrates quasidiatomic site behavior,where the introduced In causes redistribution of the electronic structure of the Co 3d states.Besides,the Al/In-PMOF(Co)layer promotes bulk charge transport and interfacial charge transfer of Si photocathode during PEC CO_(2)reduction.The Faradaic efficiency of the Si-Al/In-PMOF(Co)photocathode toward CO could increase to>90%at 0.2 V vs.RHE.Si-Al/In-PMOF(Co)photocathode also achieves a high applied bias solar-to-CO(STC)efficiency of 2.8%,which is at the state-of-the-art level.The enhanced PEC CO_(2)reduction performance is ascribed to the variation of the Fermi level of AlPMOF(Co)after the introduction of In atoms,expediting the charge transport and promoting the shift of potential of Si photocathode.Density functional theory(DFT)calculation also demonstrates that the molecular catalyst layer with quasi-diatomic sites facilitates the^(*)COOH absorption and^(*)CO desorption,thereby accelerating CO production.展开更多
The oxygen evolution reaction(OER)is the bottleneck in the overall photocatalytic splitting of water.The active sites(terminal titanium or bridging oxygen)and active species(molecular or dissociative water)of the init...The oxygen evolution reaction(OER)is the bottleneck in the overall photocatalytic splitting of water.The active sites(terminal titanium or bridging oxygen)and active species(molecular or dissociative water)of the initial step of the photocatalyzed OER on the prototypical photocatalyst TiO_(2),remain debatable.Herein,the photocatalytic chemistry of monolayer water on oxygen-pretreated TiO_(2)(110)(o-TiO_(2)(110))and reduced TiO_(2)(110)(r-TiO_(2)(110))surfaces initiated by 400 nm light illumination was investigated by time-dependent two-photon photoemission spectroscopy(TD-2PPE).The photoinduced reduction of the H_(2)O/o-TiO_(2)(110)interface rather than the H2O/r-TiO_(2)(110)interface was detected by TD-2PPE.The difference in 2PPE originated from the presence of the terminal hydroxyl anions(OHt^(-))on H_(2)O/o-TiO_(2)(110),as identified by X-ray photoelectron spectroscopy and temperature-programmed desorption.Therefore,the evolution of the electronic structure of H_(2)O/o-TiO_(2)(110)was attributed to the photocatalyzed oxidation of the terminal hydroxyl anions,which most likely formed gaseous·OH radicals,reducing the interface.This work suggested that the oxidation of hydroxyl anions on top of the terminal titanium ions on TiO_(2),which were excluded previously in solution,need to be considered in the mechanistic studies of the photocatalyzed OER.展开更多
Noble metal/titania hollow nanomaterials usually exhibit excellent photocatalytic activity because of their high specific surface area,low density,good surface permeability,strong light-harvesting capacity,and rapid i...Noble metal/titania hollow nanomaterials usually exhibit excellent photocatalytic activity because of their high specific surface area,low density,good surface permeability,strong light-harvesting capacity,and rapid interfacial charge transfer. However,the present preparation methods usually include complicated and multistep procedures,which can cause damage to the hollow nanostructures. In this paper,a facile template-induced synthesis,based on a template-directed deposition and in situ template-sacrificial dissolution,was employed to prepare Ag-modified TiO 2（Ag/TiO 2） hollow octahedra using Ag2 O octahedra as templates and TiF 4 as the precursor. In the synthetic strategy,the shells of TiO 2 hollow octahedra were formed by coating TiO 2 nanoparticles on the surface of Ag2 O templates based on the template-directed deposition. Simultaneously,the Ag2 O templates can be in situ removed by dissolving the Ag2 O octahedral template in HF solution produced via the hydrolysis reaction of TiF 4 in the reaction system. In addition,Ag nanoparticles were deposited on the inside and outside surfaces of TiO 2 shells by effectively using the photosensitive properties of Ag2 O and Ag＋ ions under light irradiation,along with the formation of TiO 2 hollow octahedra. The Ag/TiO 2 hollow octahedra exhibited high photocatalytic activity because of their（1） short diffusion distances between photogenerated electrons and holes because of the thin shells of Ag/TiO 2 hollow octahedral,（2） deposition of Ag nanoparticles on the inside and outside surfaces of TiO 2 shells,and（3） rapid interfacial charge transfer between TiO 2 shells and Ag nanoparticles. This work may also provide new insights into preparing other Ag-modified and hollow nanostructured photocatalysts.展开更多
文摘Artificial photosynthesis presents a sustainable and cost-effective approach to harnessing solar energy to produce value-added chemicals[1,2].In particular,the simultaneous photocatalytic conversion of CO_(2)and H_(2)O into formic acid(HCOOH)and hydrogen peroxide(H2O2)has emerged as a promising strategy to mitigate global warming driven by CO_(2)emissions.HCOOH is a versatile chemical and hydrogen carrier,offering economic and practical advantages due to its compatibility with existing industrial processes and energy storage/conversion systems.Meanwhile,H_(2)O_(2)is among the world’s top 100 essential chemicals,with a global market valued at$4.0 billion in 2020 and projected to grow to$5.2 billion by 2026.
基金supported by the National Natural Science Foundation of China(51972066)the Natural Science Foundation of Guangdong Province of China(2021A1515011718)the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme 2017。
文摘Severe polysulfide shuttling and sluggish sulfur redox kinetics significantly decrease sulfur utilization and cycling stability in lithium-sulfur batteries(LSBs).Herein,we develop a hollow CoO/CoP-Box core-shell heterostructure as a model and multifunctional catalyst modified on separators to induce interfacial charge modulation and expose more active sites for promoting the adsorption and catalytic conversion ability of sulfur species.Theoretical and experimental findings verify that the in-situ formed core-shell hetero-interface induces the formation of P-Co-O binding and charge redistribution to activate surface O active sites for binding lithium polysulfides(LiPSs)via strong Li-O bonding,thus strongly adsorbing with Li PSs.Meanwhile,the strong Li-O bonding weakens the competing Li-S bonding in LiPSs or Li2S adsorbed on CoO/CoP-Box surface,plus the hollow heterostructure provides abundant active sites and fast electron/Li+transfer,so reducing Li2S nucleation/dissolution activation energy.As expected,LSBs with CoO/CoP-Box modified separator and traditional sulfur/carbon black cathode display a large initial capacity of 1240 mA h g^(-1)and a long cycling stability with 300 cycles(~60.1%capacity retention)at 0.5C.Impressively,the thick sulfur cathode(sulfur loading:5.2 mg cm^(-2))displays a high initial areal capacity of 6.9 mA h cm^(-2).This work verifies a deep mechanism understanding and an effective strategy to induce interfacial charge modulation and enhance active sites for designing efficient dual-directional Li-S catalysts via engineering hollow core-shell hetero-structure.
基金National Key R&D Program of China,Grant/Award Number:2020YFA0710000National Natural Science Foundation of China,Grant/Award Numbers:22008170,21978200,22161142002,22121004。
文摘The Haber-Bosch process for industrial NH_(3) production is energy-intensive with heavy CO_(2) emissions.Electrochemical N_(2) reduction reaction(NRR)is an attractive carbon-neutral alternative for NH_(3) synthesis,while the challenge associated with N_(2) activation highlights the demand for efficient electrocatalysts.Herein,we demonstrate that PdCu nanoparticles with different Pd/Cu ratios anchored on boron nanosheet(PdCu/B)behave as efficient NRR electrocatalysts toward NH_(3) synthesis.Theoretical and experimental results confirm that the highly efficient NH_(3) synthesis can be achieved by regulating the charge transfer between interfaces and forming a symmetry-breaking site,which not only alleviates the hydrogen evolution but also changes the adsorption configuration of N_(2) and thus optimizes the reaction pathway of NRR over the separated Pd sites.Compared with monometallic Pd/B and Cu/B,the PdCu/B with the optimized Pd/Cu ratio of 1 exhibits superior activity and selectivity for NH_(3) synthesis.This study provides new insight into developing efficient catalysts for small energy molecule catalytic conversion via regulating the charge transfer between interfaces and constructing symmetry-breaking sites.
基金This work was supported by the National Natural Science Foundation of China(21822601,22176029,22172019)the Sichuan Natural Science Foundation for Distinguished Scholars(2021JDJQ0006)+2 种基金the 111 Project(B20030)the Funda-mental Research Funds for the Central Universities(ZYGX2019Z021)KHK acknowledges support made by a grant from the National Research Foundation of Korea(NRF)funded by the Ministry Of Science And ITC(MSIT)Of The Kor-ean Government(Grant No:2021R1A3B1068304).
文摘It is crucial to efficiently separate and transport photo-induced charge carriers for the effective implementation of photocatalysis toward environmental remediation.A rational design strategy is proposed to validate such proposition through the construction of an interfacial structure in the form of LDH/Zn_(2)SnO_(4) heterostructures in this research.The interfacial charge transfer on LDH/Zn_(2)SnO_(4) is greatly promoted via the unique charge transfer pathway,as characterized by transient photocurrent responses,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectrum,and photoluminescence analysis.As such,it contributes to the generation of reactive oxygen species(ROS)and the activation of reactants for the mineralization of toluene.According to the in situ DRIFTS spectra analysis,the accumulation of benzoic acid takes place possibly through the partial oxidation of the methyl group on toluene at the interface of the LDH/Zn 2 SnO 4 heterostructure.This process can greatly promote the photocatalytic oxidation of toluene with the enhanced ring-opening efficiency.The LDH/Zn 2 SnO 4 is thus demonstrated as superior photocatalyst against toluene(removal efficiency of 89.5%;mineralization of 83.1%;and quantum efficiency of 4.55×10^(−6) molecules/photon).As such,the performance of this composite far exceeds that of their individual components(e.g.,P25,pure Mg-Al LDH,or Zn_(2)SnO_(4)).This study is expected to offer a new path to the interfacial charge transfer mechanism based on the design of highly efficient photocatalysts for air purification.
基金financially supported by the National Natural Science Foundation of China(Nos.22078131 and 22108102)The Science and Technology Planning Social Development Project of Zhenjiang City(No.SH2021013)+1 种基金The Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.21KJB430036)The Jiangsu Provincial Founds for Young Scholars(No.BK20210782).
文摘The charge carrier separation efficiency and the adsorption capacity of the photocatalyst usually affect the degradation rate of antibiotics.Herein,Cerium-doped leaf-like CdS(Ce-CdS)modified with ultrathin N-doped rGO(N-rGO)composites were successfully constructed(Ce-CdS/N-rGO)to investigate the removal efficiency of tetracycline(TC).X-ray photoelectron spectroscopy(XPS)and photoelectrochemical results revealed that Ce ions doped in CdS acting as the electron capture sites facilitated the interfacial charge transfer.Theoretical calculation(DFT)results indicated that the interfacial effect between Ce-CdS and ultrathin N-rGO promoted the transfer of photogenerated electrons under the synergistic effect between the doping and interface modification strategy.The optimized Ce5-CdS/N-rGO20 composites had the maximum TC removal capability(94.5%)and maintained a stable cycling performance.In addition,the adsorption-driven photocatalytic degradation pathway of TC was studied through mass spectrometry(MS)and in-situ Fourier transform infrared spectroscopy(in-situ FTIR).This study will provide an effective strategy for the construction of efficient photocatalytic composites for wastewater treatment.
基金financially supported by the Natural Science Foundation of China (Grants 51802253, 51972172, 61705102,61904152, and 91833304)the China Postdoctoral Science Foundation (Grant 2021M692630)+6 种基金the Natural Science Basic Research Plan in Shaanxi Province of China (2019JM-326)the Joint Research Funds of Department of Science&Technology of Shaanxi Province and Northwestern Polytechnical University (No. 2020GXLH-Z-007)the Natural Science Foundation of Jiangsu Province for Distinguished Young Scholars,China (Grant BK20200034)the Young 1000 Talents Global Recruitment Program of Chinathe Jiangsu Specially Appointed Professor programthe “Six talent peaks” Project in Jiangsu Province,Chinathe Fundamental Research Funds for the Central Universities。
文摘Pb-free Sn-based perovskite solar cells(PSCs) have recently made inspiring progress, and power conversion efficiency(PCE) of 14.8% has been achieved. However, due to the energy-level mismatch and poor interfacial contact between commonly used hole transport layer(i.e., poly(3,4-ethylenedioxythio phene):poly(styrene sulfonate), PEDOT:PSS) and FASnI_(3) film, it is still challenging to effectively extract holes at the interface. Owing to the p-type nature of Sn-based perovskites, the efficient hole extraction is of particular significance to improve the PCE of their solar cells. In this work, for the first time, the role of chiral cations, a-methylbenzylamine(S-/R-/rac-MBA), in promoting hole transportation of FASnI_(3)-based PSCs is demonstrated. The introduction of MBAs is found to form 2D/3D film with lowdimensional structures locating at PEDOT:PSS/FASnI_(3) interface, which facilitates the energy level alignment and efficient charge transfer at the interface. Importantly, chiral-induced spin selectivity(CISS)effect of R-MBA_(2)SnI_(4)induced by chiral R-MBA cation is found to further assist the specific interfacial transport of accumulated holes. As a result, R-MBA-based PSCs achieve decent PCE of 10.73% with much suppressed hysteresis and enhanced device stability. This work opens up a new strategy to efficiently promote the interfacial extraction of accumulated charges in working PSCs.
文摘Although photocatalytic water splitting has excellent potential for converting solar energy into chemical energy,the challenging charge separation process and sluggish surface catalytic reactions significantly limit progress in solar energy conversion using semiconductor photocatalysts.Herein,we demonstrate a feasible strategy involving the surface assembly of cobalt oxide species(CoO_(x))on a visible-light-responsive Cd_(0.9)Zn_(0.1)S(CZS)photocatalyst to fabricate a hierarchical CZS@CoO_(x) heterostructure.The unique hierarchical structure effectively accelerates the directional transfer of photogenerated charges,reducing charge recombination through the smooth interfacial heterojunction between CZS and CoO_(x),as evidenced by photoluminescence(PL)spectroscopy and various electrochemical characterizations.The surface cobalt species on the CZS material also act as efficient cocatalysts for photocatalytic hydrogen production,with activity even higher than that of noble metals.The well-defined CZS@CoO_(x) heterostructure not only enhances the interfacial separation of photoinduced charges,but also improves surface catalytic reactions.This leads to superior photocatalytic performances,with an apparent quantum efficiency of 20%at 420 nm for visible-light-driven hydrogen generation,which is one of the highest quantum efficiencies measured among noble-metal-free photocatalysts.Our work presents a potential pathway for controlling complex charge separation and catalytic reaction processes in photocatalysis,guiding the practical development of artificial photocatalysts for successful transformation of solar to chemical energy.
基金Supported by the National Natural Science Foundation of China (Grant No.22002031)the Natural Science Foundation of Zhejiang Province (Grant No.LY18F010019)the Innovation Project in Hangzhou for Returned Scholar。
文摘The modulation of electrical properties of MoS_2 has attracted extensive research interest because of its potential applications in electronic and optoelectronic devices.Herein,interfacial charge transfer induced electronic property tuning of MoS_2 are investigated by in situ ultraviolet photoelectron spectroscopy and x-ray photoelectron spectroscopy measurements.A downward band-bending of MoS_2-related electronic states along with the decreasing work function,which are induced by the electron transfer from Cs overlayers to MoS_2,is observed after the functionalization of MoS_2 with Cs,leading to n-type doping.Meanwhile,when MoS_2 is modified with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane(F_4-TCNQ),an upward band-bending of MoS_2-related electronic states along with the increasing work function is observed at the interfaces.This is attributed to the electron depletion within MoS_2 due to the strong electron withdrawing property of F_4-TCNQ,indicating p-type doping of MoS_2.Our findings reveal that surface transfer doping is an effective approach for electronic property tuning of MoS_2 and paves the way to optimize its performance in electronic and optoelectronic devices.
基金supported by the National Natural Science Foundation of China(52373087,51973235,52173091,22208331 and 62274050)Program for Leading Talents of National Ethnic Affairs Commission of China(MZR21001)+2 种基金Hubei Provincial Natural Science Foundation of China(2021CFA022)Wuhan Science and Technology Bureau(2020010601012198)Zhejiang Provincial Natural Science Foundation of China under Grant No.LZ21E020002.
文摘Bismuth vanadate(BiVO_(4))is a promising photoanode material for photoelectrochemical(PEC)water oxidation.However,its performance is greatly hindered by poor bulk and interfacial charge transfer.Herein,to address this issue,iron doped vanadyl phosphate(Fe:VOPO_(4))was grafted on molybdenum doped BiVO_(4)(Mo:BiVO_(4))for significantly enhancing charge transfer and oxygen evolution kinetics simultaneously.Consequently,the resultant Fe:VOPO_(4)/Mo:BVO_(4) photoanode exhibits a remarkable photocurrent density of 6.59 mA cm^(-2) at 1.23 V versus the reversible hydrogen electrode(VRHE)under AM 1.5G illumination,over approximately 5.5 times as high as that of pristine BiVO_(4).Systematic studies have demonstrated that the hopping activation energy of small polarons is significantly reduced due to the Mo doping,resulting in accelerated bulk charge transfer.More importantly,the deposition of Fe:VOPO_(4) promotes the interfacial charge transfer between Mo:BiVO_(4) and Fe:VOPO_(4) via the construction of V-O-V and P-O bonds,in addition to facilitating water splitting kinetics.This work provides a general strategy for optimizing charge transfer process,especially at the interface between photoanodes and cocatalysts.
基金supported by the National Natural Science Foundation of China(52471203,12174237,52171183)the Fundamental Research Program of Shanxi Province(202303021221152)the Natural Science Foundation of Tianjin(23JCZDJC01210).
文摘In strongly correlated transition metal oxide(TMO)systems,the anomalous Hall effect(AHE)can not only reveal the underlying physical mechanism of the coupling between multiple degrees of freedom,but also generate spin current-driven magnetization switching.However,enhancing the AHE in this system remains a significant challenge at present.This work systematically investigates the electronic transport properties of SrIrO_(3)/NiCo_(2)O_(4)(SIO/NCO)heterostructures,showing that the AHE of SIO/NCO heterostructures is enhanced by an order of magnitude compared to the ferrimagnetic NCO single film.The enhancement of AHE is more significant as the thickness of the SIO sublayer decreases,which is attributed to the fact that large strain exacerbates the interfacial charge transfer.This is demonstrated through the variation of binding energies and concentrations of electronic states in the X-ray photoelectron spectroscopy.Moreover,the AHE in SIO/NCO heterostructures arises from the synergistic effect of the intrinsic mechanism dominated by Berry curvature and the extrinsic mechanism caused by impurity scattering.This finding paves the way for advancing the reliability of TMO-based spintronic devices.
文摘Correction to:Nano-Micro Letters(2025)17:117 https://doi.org/10.1007/s40820-025-01660-0 Following publication of the original article[1],the authors reported that the supplementary file needed to be updated because they mistakenly used the incorrect version.The original article[1]has been corrected.
基金the Natural Science research project of Universities in Anhui Province(No.KJ2021ZD0001)the Natural Science Foundation of Anhui Province(No.2208085MB20)the National Natural Science Foundation of China(No.22101001).
文摘The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.
基金supported by the National Natural Science Foundation of China(Nos.52273110,21975191,52372271,22173070)the Knowledge Innovation Program of Wuhan Shuguang Project,and the Fundamental Research Funds for the Central Universities(WUT:2023Ⅲ013GX).
文摘The impact of interfacial charge on catalytic performance of supported-metal-cluster(SMC)heterostructures remains unclear,hindering efforts to develop high-performance SMC catalysts.Herein we systematically investigated interfacial charge effects of SMCs using a model system of graphene-supported gold-nanoclusters(AuNCs/rGO)for azo hydrogenation.Three types of SMCs with different interfacial charges were synthesized by anchoring electropositive 2-aminoethanethiol(CSH),amphoteric cysteine(Cys),and electronegative 3-mercaptopropionic-acid(MPA)onto AuNCs/rGO,respectively.All three SMCs exhibited high and selective catalytic activity to azo-hydrogenation in four representative azo dyes.The catalytic activity of Cys@AuNCs/rGO was lower than that of CSH@AuNCs/rGO but higher than that of MPA@AuNCs/rGO.However,the cyclic stability of Cys@AuNCs/rGO was inferior to that of both CSH@AuNCs/rGO and MPA@AuNCs/rGO.Further mechanistic studies revealed that amino ligands modified CSH@AuNCs and Cys@AuNCs agglomerated into large-size gold nanoparticles on rGO surface during catalytic reaction under NaBH_(4) action,leading to reduced efficiency and cyclic stability.Conversely,non-amino ligand modified MPA@AuNCs only partially detached from rGO surface without agglomeration,resulting in better cyclic stability.Protection of amino groups in ligands such as modifying-NH_(3)^(+)group in Cys into imine to form N-isobutyryl-L-cysteine(NIBC)substantially improved the cyclic stability while maintaining the high activity in the NIBC@AuNCs/rGO catalyst system.Our work provides an approach for developing a highly-active and stable SMC heterostructure catalyst via manipulating interfacial charges in SMC.
基金financially supported by the National Natural Science Foundation of China(No.52002270)the China Postdoctoral Science Foundation(No.2020M670661)。
文摘The interfacial characteristics of the Li metal anode(LMA)play a crucial role in its overall performance.Despite various materials being applied to modify the interface,a comprehensive understanding of their specific mechanisms remains to be investigated.Herein,we have prepared carbon cloth(CC)frameworks with their surfaces modified using ferromagnetic metal/LiF heterogeneous films(T^(M)-LiF-CC)as the substrate for LMA,which exhibit superior electrochemical performance.Utilizing ferromagnetic Co as a representative example,our study demonstrates that the enhanced performance of Co-LiF-CC,compared to bare CC,is attributed to the spinpolarized interface contributed by the Co/LiF heterostructure.Co and LiF play individual roles in redistributing electrons and Li^(+)to promote homogeneous Li deposition.Co nanoparticles play a crucial role in generating strong surface capacitance by storing electrons in spin-split bands,while LiF,with low surface diffusion barriers,ensures fast transportation of Li^(+).The Co-LiF-CC@Li electrodes deliver long lives of 7400 and 3600 h at 1 and 2 mA·cm^(-2)in symmetric cells,respectively;moreover,they enable full batteries with high and durable capacities,particularly when the N/P ratios are low(3.3 or even 1.7).
基金support by the Award Program for Minjiang Scholar Professorshipfinancially supported by the National Natural Science Foundation of China(Nos.21703038,22072025)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR147)。
文摘Atomically precise metal nanoclusters(NCs)have been deemed as an emerging class of metal nanomaterials owing to fascinating size-dependent physicochemical properties,discrete energy band structure,and quantum confinement effect,which are distinct from conventional metal nanoparticles(NPs).Nevertheless,metal NCs suffer from photoinduced self-oxidative aggregation accompanied by in-situ transformation to metal NPs,markedly reducing the photosensitization of metal NCs.Herein,maneuvering the generic instability of metal NCs,we perform the charge transport impetus comparison between atomically precise metal NCs and plasmonic metal NPs counterpart obtained from in-situ self-transformation of metal NCs in photoelectrochemical(PEC)water splitting reaction.For conceptual demonstration,we proposed two quintessential heterostructures,which include TNTAs-Au_(25)heterostructure fabricated by electrostatically depositing glutathione(GSH)-protected Au_(25)(GSH)_(18)NCs on the TiO_(2)nanotube arrays(TNTAs)substrate,and TNTAs-Au heterostructure constructed by triggering self-transformation of Au_(25)(GSH)_(18)NCs to plasmonic Au NPs in TNTAs-Au_(25)via calcination.The results indicate that photoelectrons produced over Au_(25)NCs are superior to hot electrons of plasmonic Au NPs in stimulating the interracial charge transport toward solar water oxidation.This is mainly ascribed to the significantly accelerated carrier transport kinetics,prolonged carrier lifespan,and substantial photosensitization effect of Au_(25)NCs compared with plasmonic Au NPs,resulting in the considerably enhanced PEC water splitting performance of TNTAs-Au_(25)relative to plasmonic TNTAs-Au counterpart under visible light irradiation.Our work would provide important implications for rationally designing atomically precise metal NCsbased photosystems toward solar energy conversion.
基金Supported by the National Natural Science Foundation of China
文摘The present paper covers the lipid-free rhodium tetrasulfonato-phthalocyanine (RhTSPc) films prepared on p-Si(111) by using Langmuir-Blodgett technique. Their surface photovoltage spectra were measured. It was found that there is a strong interaction at the interface between the RhTSPc film and p-Si (111) and that the surface photovoltaic effect of the film system is maximum when only one monolayer of RhTSPc molecules coats p-Si(111), which is similar to that of CuTSPc films on p-Si(111) reported previously. These results confirm that only the monolayer of dye molecules being adjacent to the semiconductor surface plays a key role in the light-induced interfacial charge transfer process.
基金supported by the Fundamental Re-search Funds for the Central Universities(Ganglong Cui)and National Key Research and Development Pro-gram of China(No.2021YFA1500703 to Ganglong Cui)National Natural Science Foundation of China(No.22103067 to Xiao-Ying Xie)and Natural Science Foundation of Shandong Province(No.ZR2021QB105 to Xiao-Ying Xie).
文摘Heterostructures of organic semi-conductors and transition metal dichalcogenides(TMDs)are viable candidates for superior optoelec-tronic devices.Photoinduced inter-facial charge transfer is crucial for the performance efficiency of such devices,yet the underlying mecha-nism,especially the roles of optical-ly dark triplets and spatially sepa-rated charge transfer states,is poorly understood.In the present work,we obtain the struc-tures of distinct excited states and investigate how they are involved in the charge transfer process at the Pd-octaethylporphyrin(PdOEP)and WS_(2) interface in terms of their energies and couplings.The results show that electron transfer from the triplet PdOEP formed via intersystem crossing prevails over direct electron transfer from the singlet(two orders of magnitude faster).Further analysis reveals that the relatively higher rate of triplet electron transfer compared to singlet electron transfer is mainly attributed to a smaller reorganization energy,which is dominated by the out-of-plane vibrations of the organic component.The work emphasizes the important roles of the optically dark triplets in the electron transfer of the PdOEP@WS_(2) heterostructure,and provides valuable theoretical insights for further improv-ing the optoelectronic performance of TMD-based devices.
基金supported by the National Natural Science Foundation of Hunan Province(2025JJ60094)the Hunan Provincial Natural Science Foundation for Distinguished Young Scholars(2025JJ20019)the National Natural Science Foundation of China(22078368)。
文摘The photoelectrocatalytic(PEC)CO_(2)reduction process includes photogenerated charge transport,multiphase interface,intermediate adsorption,and chemical bonding transformation,all of which are closely associated with the interface and surface layer on the photocathode.However,it is difficult to design the photocathode with an effective interface and surface active site for realizing the highly selective PEC CO_(2)reduction at ultralow potential.Here,we design a novel semiconductor p-n junction comprising Si nanowires and an indium-edited porphyrin-based metal-organic framework{Al/In-PMOF(Co)}for efficient CO_(2)reduction.The Al/In-PMOF(Co)catalyst containing In and Co metal atoms demonstrates quasidiatomic site behavior,where the introduced In causes redistribution of the electronic structure of the Co 3d states.Besides,the Al/In-PMOF(Co)layer promotes bulk charge transport and interfacial charge transfer of Si photocathode during PEC CO_(2)reduction.The Faradaic efficiency of the Si-Al/In-PMOF(Co)photocathode toward CO could increase to>90%at 0.2 V vs.RHE.Si-Al/In-PMOF(Co)photocathode also achieves a high applied bias solar-to-CO(STC)efficiency of 2.8%,which is at the state-of-the-art level.The enhanced PEC CO_(2)reduction performance is ascribed to the variation of the Fermi level of AlPMOF(Co)after the introduction of In atoms,expediting the charge transport and promoting the shift of potential of Si photocathode.Density functional theory(DFT)calculation also demonstrates that the molecular catalyst layer with quasi-diatomic sites facilitates the^(*)COOH absorption and^(*)CO desorption,thereby accelerating CO production.
基金supported by the National Key Research and Development Program of China(No.2021YFA1500601)the National Natural Science Foundation of China(Nos.22322306 and 22288201)+3 种基金the Chinese Academy of Sciences(Nos.YSBR007,XDB0970000)the Key Research Project of Shaanxi Provincial Science and Technology Department(No.2023-YBNY-158)the Xi’an Science and Technology Project(No.22NYYF016)the 111 Project。
文摘The oxygen evolution reaction(OER)is the bottleneck in the overall photocatalytic splitting of water.The active sites(terminal titanium or bridging oxygen)and active species(molecular or dissociative water)of the initial step of the photocatalyzed OER on the prototypical photocatalyst TiO_(2),remain debatable.Herein,the photocatalytic chemistry of monolayer water on oxygen-pretreated TiO_(2)(110)(o-TiO_(2)(110))and reduced TiO_(2)(110)(r-TiO_(2)(110))surfaces initiated by 400 nm light illumination was investigated by time-dependent two-photon photoemission spectroscopy(TD-2PPE).The photoinduced reduction of the H_(2)O/o-TiO_(2)(110)interface rather than the H2O/r-TiO_(2)(110)interface was detected by TD-2PPE.The difference in 2PPE originated from the presence of the terminal hydroxyl anions(OHt^(-))on H_(2)O/o-TiO_(2)(110),as identified by X-ray photoelectron spectroscopy and temperature-programmed desorption.Therefore,the evolution of the electronic structure of H_(2)O/o-TiO_(2)(110)was attributed to the photocatalyzed oxidation of the terminal hydroxyl anions,which most likely formed gaseous·OH radicals,reducing the interface.This work suggested that the oxidation of hydroxyl anions on top of the terminal titanium ions on TiO_(2),which were excluded previously in solution,need to be considered in the mechanistic studies of the photocatalyzed OER.
基金supported by the National Natural Science Foundation of China(5120839621277107+5 种基金21477094and 51472192)the Program for New Century Excellent Talents in University(NCET-13-0944)the Fundamental Research Funds for the Central Universities(WUT 2014-1a-0032014-VII-037and 2015IB002)~~
文摘Noble metal/titania hollow nanomaterials usually exhibit excellent photocatalytic activity because of their high specific surface area,low density,good surface permeability,strong light-harvesting capacity,and rapid interfacial charge transfer. However,the present preparation methods usually include complicated and multistep procedures,which can cause damage to the hollow nanostructures. In this paper,a facile template-induced synthesis,based on a template-directed deposition and in situ template-sacrificial dissolution,was employed to prepare Ag-modified TiO 2（Ag/TiO 2） hollow octahedra using Ag2 O octahedra as templates and TiF 4 as the precursor. In the synthetic strategy,the shells of TiO 2 hollow octahedra were formed by coating TiO 2 nanoparticles on the surface of Ag2 O templates based on the template-directed deposition. Simultaneously,the Ag2 O templates can be in situ removed by dissolving the Ag2 O octahedral template in HF solution produced via the hydrolysis reaction of TiF 4 in the reaction system. In addition,Ag nanoparticles were deposited on the inside and outside surfaces of TiO 2 shells by effectively using the photosensitive properties of Ag2 O and Ag＋ ions under light irradiation,along with the formation of TiO 2 hollow octahedra. The Ag/TiO 2 hollow octahedra exhibited high photocatalytic activity because of their（1） short diffusion distances between photogenerated electrons and holes because of the thin shells of Ag/TiO 2 hollow octahedral,（2） deposition of Ag nanoparticles on the inside and outside surfaces of TiO 2 shells,and（3） rapid interfacial charge transfer between TiO 2 shells and Ag nanoparticles. This work may also provide new insights into preparing other Ag-modified and hollow nanostructured photocatalysts.
