Modified TiO_(2)/In_(2)O_(3) heterojunction with efficient charge separation for visible-light-driven photocatalytic CO_(2) reduction to C_(2) product

Utilizing sunlight to convert CO_(2) into chemical fuels could address the greenhouse effect and fossil fuel crisis,Heterojunction structure catalysts with oxygen vacancy are attractive in the field of photocatalytic CO_(2) conversion.Herein,a modified TiO_(2)/In_(2)O_(3)(R-P2 5/In_(2)O_(3-x)) type Ⅱ heterojunction composite with oxygen vacancies is designed for photocatalytic CO_(2) reduction,which exhibits excellent CO_(2) reduction activity,with a C_(2) selectivity of 56.66%(in terms of R_(electron)).In situ Fourier-transform infrared spectroscopy(DRIFTS) and time-resolved photoluminescence(TR-PL) spectroscopy are used to reveal the intermediate formation of the photocatalytic mechanism and photogenerated electron lifetime,respectively.The experimental characterizations reveal that the R-P25/In_(2)O_(3-x) composite shows a remarkable behavior for coupling C-C bonds.Besides,efficient charge separation contributes to the improved CO_(2) conversion performance of photocatalysts.This work introduces a type Ⅱ heterojunction composite photocatalyst,which promotes understanding the CO_(2) reduction mechanisms on heterojunction composites and is valuable for the development of photocatalysts.

Modulating charge separation and transfer for high-performance photoelectrodes via built-in electric field

Constructing a built-in electric field has emerged as a key strategy for enhancing charge separation and transfer,thereby improving photoelectrochemical performance.Recently,considerable efforts have been devoted to this endeavor.This review systematically summarizes the impact of built-in electric fields on enhancing charge separation and transfer mechanisms,focusing on the modulation of built-in electric fields in terms of depth and orderliness.First,mechanisms and tuning strategies for built-in electric fields are explored.Then,the state-of-the-art works regarding built-in electric fields for modulating charge separation and transfer are summarized and categorized according to surface and interface depth.Finally,current strategies for constructing bulk built-in electric fields in photoelectrodes are explored,and insights into future developments for enhancing charge separation and transfer in high-performance photoelectrochemical applications are provided.

Long-range electron synergy over Pt_(1)-Co_(1)/CN bimetallic single-atom catalyst in enhancing charge separation for photocatalytic hydrogen production

The development of novel single-atom catalysts with optimal electron configuration and economical noble-metal cocatalyst for efficient photocatalytic hydrogen production is of great importance,but still challenging.Herein,we fabricate Pt and Co single-atom sites successively on polymeric carbon nitride(CN).In this Pt_(1)-Co_(1)/CN bimetallic single-atom catalyst,the noble-metal active sites are maximized,and the single-atomic Co_(1)N_4sites are tuned to Co_(1)N_3sites by photogenerated electrons arising from the introduced single-atomic Pt_(1)N_4sites.Mechanism studies and density functional theory(DFT)calculations reveal that the 3d orbitals of Co_(1)N_3single sites are filled with unpaired d-electrons,which lead to the improved visible-light response,carrier separation and charge migration for CN photocatalysts.Thereafter,the protons adsorption and activation are promoted.Taking this advantage of long-range electron synergy in bimetallic single atomic sites,the photocatalytic hydrogen evolution activity over Pt_(1)-Co_(1)/CN achieves 915.8 mmol g^(-1)Pt h^(-1),which is 19.8 times higher than Co_(1)/CN and 3.5 times higher to Pt_(1)/CN.While this electron-synergistic effect is not so efficient for Pt nanoclusters.These results demonstrate the synergistic effect at electron-level and provide electron-level guidance for the design of efficient photocatalysts.

Time-resolved photoluminescence of anatase/rutile TiO_2 phase junction revealing charge separation dynamics

Junctions are an important structure that allows charge separation in solar cells and photocatalysts. Here, we studied the charge transfer at an anatase/rutile TiO2 phase junction using time-resolved photoluminescence spectroscopy. Visible （-S00 nm） and near-infrared （NIR, -830 nm） emissions were monitored to give insight into the photoinduced charges of anatase and rutile in the junction, respectively, New fast photoluminescence decay components appeared in the visible emission of futile-phase dominated TiO2 and in the NIR emission of many mixed phase TiO2samples. The fast decays confirmed that the charge separation occurred at the phase junction. The visible emission intensity from the mixed phase TiO2 increased, revealing that charge transfer from rutile to anatase was the main pathway. The charge separation slowed the microsecond time scale photolumines- cence decay rate for charge carriers in both anatase and rutile. However, the millisecond decay of the charge carriers in anatase TiO2 was accelerated, while there was almost no change in the charge carrier dynamics of rutile TiO2. Thus, charge separation at the anatase/rutile phase junction caused an increase in the charge carrier concentration on a microsecond time scale, because of slower electron-hole recombination. The enhanced photocatalytic activity previously observed at ana- tase/rutile phase junctions is likely caused by the improved charge carrier dynamics we report here. These findings may contribute to the development of improved photocatalytic materials.

Multichannel charge separation promoted ZnO /P25 heterojunctions for the photocatalytic oxidation of toluene

The fabrication of multicomponent heterojunctions is an effective strategy to improve the performance of TiO2 based photocatalysts. We provide a new strategy for improving the charge separation and photocatalytic performance of ZnO /TiO2 composites by the formation of multichannel charge separated heterojunctions. ZnO /P25 composites were prepared by an incipient wetness impregnation method, and applied for the photocatalytic destruction of gaseous toluene. The ZnO /P25 composites consist of anatase TiO2（ATiO2）, rutile TiO2（RTiO2） and hexagonal zincite structures. The parasitic phase of ZnO in P25 leads to the formation of ZnO（002）/ATiO2（101）/RTiO2（110） heterojunctions that exhibit enhanced light absorption and improved multichannel electron/hole separation. ZnO /P25 heterojunctions can completely oxidize toluene into CO2 and H2O under ultraviolet light irradiation at room temperature, and show enhanced photocatalytic activity in comparison with P25 owing to the efficient electron-hole separation. Such a multichannel charge separated design strategy may provide new insight into the design of highly effective photocatalysts and their potential technological applications.

Solar energy conversion on g-C3N4 photocatalyst:Light harvesting,charge separation,and surface kinetics

Photocatalysis. which utilizes solar energy to trigger chemical reactions, is one of the most desirable solar-energy-conversion approaches. Graphitic carbon nitride （g-C3N4）. as an attractive metal-free photocatalyst, has drawn worldwide research interest in the area of solar energy conversion due to its easy synthesis, earth-abundant nature, physicochemical stability and visible-light-responsive properties. Over the past ten years, g-C3N4 based photocatalysts have experienced intensive exploration, and great progress has been achieved. However, the solar conversion efficiency is still far from industrial applications due to the wide bandgap, severe charge recombination, and lack of surface active sites. Many strategies have been proposed to enhance the light absorption, reduce the recombination of charge carriers and accelerate the surface kinetics. This work makes a crucial review about the main contributions of various strategies to the light harvesting, charge separation and surface kinetics of g-C3N4 photocatalyst. Furthermore, the evaluation measurements for the enhanced light harvesting, reduced charge recombination and accelerated surface kinetics will be discussed. In addition, this review proposes future trends to enhance the photocatalytic performance of g-C3N4 photocatalyst for the solar energy conversion.

SrTiO3/BiOI heterostructure: Interfacial charge separation, enhanced photocatalytic activity, and reaction mechanism

Heterostructured photocatalysts provide an effective way to achieve enhanced photocatalytic performances through efficient charge separation.Although both wide-and narrow-band-gap photocatalysts have been widely investigated,the charge separation and transfer mechanism at the contacting interface of the two has not been fully revealed.Here,a novel SrTiO3/BiOI(STB)heterostructured photocatalyst was successfully fabricated by using a facile method.The heterostructure in the photocatalyst extends the photoabsorption to the visible light range,and thus,high photocatalytic NO removal performance can be achieved under visible light irradiation.A combination of experimental and theoretical evidences indicated that the photogenerated electrons from the BiOI semiconductor can directly transfer to the SrTiO3 surface through a preformed electron delivery channel.Enhanced electron transfer was expected between the SrTiO3 and BiOI surfaces under light irradiation,and leads to efficient ROS generation and thus a high NO conversion rate.Moreover,in situ diffused reflectance infrared Fourier transform spectroscopy revealed that STB can better inhibit the accumulation of the toxic intermediate NO2 and catalyze the NO oxidation more effectively.This work presents a new insight into the mechanism of the interfacial charge separation in heterostructures and provides a simple strategy to promote the photocatalytic technology for efficient and safe air purification.

Construction of NH2-MIL-125(Ti)/Bi2WO6 composites with accelerated charge separation for degradation of organic contaminants under visible light irradiation

Photocatalysis is considered as an ideal strategy for water pollution treatment.However,it remains challenging to design a highly efficient photo-catalytic system through regulating the charge flow via a precise approach.In this work,a novel NH2-MIL-125(Ti)/Bi2WO6 composite was constructed via self-assembly growing Bi2WO6 nanosheets on NH2-MIL-125(Ti)material.The characterization results demonstrated that NH2-MIL-125(Ti)was successfully incorporated into Bi2WO6 and the photoexcited carriers could be efficiently separated and transferred between the two components.NH2-MIL-125(Ti)/Bi2WO6 composites displayed enhanced photocatalytic activity for the removal of rhodamine B(RhB)and tetracycline(TC)under visible light irradiation,and the optimal weight ratio of NH2-MIL-125(Ti)was determined to be 7 wt%.The introduction of NH2-MIL-125(Ti)into Bi2WO6 could raise the absorption of visible light,accelerate the separation and transfer of charge carriers,and boost photocatalytic activity.This research presents a wide range of possibilities for the further development of novel composites in the field of environment purification.

In situ fabrication of CdMoO4/g-C3N4 composites with improved charge separation and photocatalytic activity under visible light irradiation

To further improve the charge separation and photocatalytic activities of g-C3N4 and CdMoO4 under visible light irradiation,CdMoO4/g-C3N4 composites were rationally synthesized by a facile precipitation-calcination procedure.The crystal phases,morphologies,chemical compositions,textural structures,and optical properties of the as-prepared composites were characterized by the corresponding analytical techniques.The photocatalytic activities toward degradation of rhodamine B solution were evaluated under visible light irradiation.The results revealed that integrating CdMoO4 with g-C3N4 could remarkably improve the charge separation and photocatalytic activity,compared with those of pristine g-C3N4 and CdMoO4.This would be because the CdMoO4/g-C3N4 composites could facilitate the transfer and separation of the photoexcited electron-hole pairs,which was confirmed by electrochemical impedance spectroscopy,transient photocurrent responses,and photoluminescence measurements.Moreover,active species trapping experiments demonstrated that holes(h+)and superoxide radicals(?O2?)were the main active species during the photocatalytic reaction.A possible photocatalytic mechanism was proposed on the basis of the energy band structures determined by Mott-Schottky tests.This work would provide further insights into the rational fabrication of composites for organic contaminant removal.

Construction of nitrogen and phosphorus co-doped graphene quantum dots/Bi5O7I composites for accelerated charge separation and enhanced photocatalytic degradation performance

Nitrogen and phosphorus co-doped graphene quantum dot-modified Bi5O7 I(NPG/Bi5O7 I)nanorods were fabricated via a simple solvothermal method.The morphology,structure,and optical properties of the as-prepared samples were investigated by X-ray diffraction,scanning electron microscopy,high-resolution transmission electron microscopy,X-ray photoelectron spectroscopy(XPS),and diffused reflectance spectroscopy.The photocatalytic performance was estimated by degrading the broad-spectrum antibiotics tetracycline and enrofloxacin under visible light irradiation.The photodegradation activity of Bi5O7 I improved after its surface was modified with NPGs,which was attributed to an increase in the photogenerated charge transport rate and a decrease in the electron-hole pair recombination efficiency.From the electron spin resonance spectra,XPS valence band data,and free radical trapping experiment results,the main active substances involved in the photocatalytic degradation process were determined to be photogenerated holes and superoxide radicals.A possible photocatalytic degradation mechanism for NPG/Bi5O7 I nanorods was proposed.

Surface defect-rich ceria quantum dots anchored on sulfur-doped carbon nitride nanotubes with enhanced charge separation for solar hydrogen production

Designing defect-engineered semiconductor heterojunctions can effectively promote the charge carrier separation.Herein,novel ceria(CeO2) quantum dots(QDs) decorated sulfur-doped carbon nitride nanotubes(SCN NTs) were synthesized via a thermal polycondensation coupled in situ depositionprecipitation method without use of template or surfactant.The structure and morphology studies indicate that ultrafine CeO2 QDs are well distributed inside and outside of SCN NTs offering highly dispersed active sites and a large contact interface between two components.This leads to the promoted formation of rich Ce^(3+) ion and oxygen vacancies as confirmed by XPS.The photocatalytic performance can be facilely modulated by the content of CeO2 QDs introduced in SCN matrix while bare CeO2 does not show activity of hydrogen production.The optimal catalyst with 10% of CeO2 loading yields a hydrogen evolution rate of 2923.8 μmol h-1 g-1 under visible light,remarkably higher than that of bare SCN and their physical mixtures.Further studies reveal that the abundant surface defects and the created 0 D/1 D junctions play a critical role in improving the separation and transfer of charge carriers,leading to superior solar hydrogen production and good stability.

Tip-induced directional charge separation on one-dimensional BiVO4 nanocones for asymmetric light absorption

One dimensional(1D)semiconductor is a class of extensively attractive materials for many emerging solar energy conversion technologies.However,it is still of shortage to assess the impact of 1D structural symmetry on spatial charge separation and understand its underlying mechanism.Here we take controllably-synthesized 1D BiVO_(4)nanocones and nanorods as prototypes to study the influence of 1D symmetry on charge separation.It is found that the asymmetric BiVO_(4)nanocones enable more effective charge separation compared with the symmetric nanorods.The unexpected spatial charge separation on the nanocones is mainly ascribed to uneven light absorption induced diffusion-controllable charge separation due to symmetry breaking of 1D nanostructure,as evidenced by spatial and temporal resolved spectroscopy.Moreover,the promotion effect of charge separation on the nanocones was quantitatively evaluated to be over 20 times higher than that in BiVO_(4)nanorods.This work gives the first demonstration of the influence of 1D structural symmetry on the charge separation behavior,providing new insights to design and fabricate semiconductor materials for efficient solar energy conversion.

EPR study of charge separation associated states and reversibility of surface bound superoxide radicals in SrTiO_(3) photocatalyst

Understanding the processes of charge generation, transfer and capture is important for the design and synthesis of efficient photocatalysts. In this work, light-induced charge separation and effect of O_(2) on electron transfer processes in SrTiO_(3) were investigated by electron paramagnetic resonance(EPR). It was found that photoinduced electron transfer from O_(2)- to Ti^(4+) produced Ti^(3+) and O- redox radical pairs under vacuum condition. Under oxygen atmosphere, however, surface bound superoxide radicals O_(2)-were formed by electron reduction of adsorbed oxygen at initial photoirradiation stage, and quenched by the reverse electron transfer to Ti^(4+) upon further photoirradiation. Formation of long-lived charge separation associated [Ti^(3+)---O-] species and the reversibility of surface bound superoxide radicals mediating the processes of photogenerated electrons may be accountable for the high activity of SrTiO_(3) in photocatalytic water splitting reaction.

Modulating charge separation and transfer kinetics in carbon nanodots for photoredox catalysis

Artificial photosynthesis has gained increasing interest as a promising solution to the worldwide energy and environmental issues. A crucial requirement for realizing a sustainable system for artificial photosynthesis is to explore low cost, highly-efficient and stable photoactive materials. Carbon nanodots(CNDs) have attracted considerable attention owing to their low cost, tunable chemistry and unique light-harvesting capability. Previous review articles have highlighted the photocatalytic and photoelectrocatalytic applications of CNDs and CNDs-based composite photocatalysts. However, the control of the separation and transfer processes of photogenerated electron/hole pairs in CNDs has not been reviewed.This review summarizes the recent progress in the design of CNDs as new light-harvesting materials and highlights their applications in photocatalytic hydrogen production, CO2 photoreduction and environmental remediation. Strategies that have been employed to modulate the separation and transfer kinetics of photogenerated charge carriers in CNDs are discussed in detail. The challenges and new directions in this emerging area of research are also proposed.

Energy funneling and charge separation in CdS modified with dual cocatalysts for enhanced H_(2) generation

Anchoring molecular cocatalysts on semiconductors has been recognized as a general strategy to boost the charge separation efficiency required for efficient photocatalysis.However,the effect of molecular cocatalysts on energy funneling(i.e.,directional energy transfer)inside semiconductor photocatalysts has not been demonstrated yet.Here we prepared CdS nanorods with both thin and thick rods and anchored the conjugated molecules 2‐mercaptobenzimidazole(MBI)and cobalt molecular catalysts(MCoA)sequentially onto the surface of nanorods.Transient absorption measurements revealed that MBI molecules facilitated energy funneling from thin to thick rods by the electronic coupling between thin and thick nanorods,which is essentially a light‐harvesting antenna approach to enhance the charge generation efficiency in the reaction center(here the thick rods).Moreover,MBI and MCoA molecules selectively extracted photogenerated holes and electrons of CdS nanorods rapidly,leading to efficient charge separation.Consequently,CdS/MBI/MCoA displayed 15 times enhanced photocatalytic H_(2) evolution(1.65 mL)than pure CdS(0.11 mL)over 3 h of illumination.The amount of H_(2) evolution reached 60 mL over 48 h of illumination with a high turnover number of 26294 and an apparent quantum efficiency of 71%at 420 nm.This study demonstrates a novel design principle for next‐generation photocatalysts.

Surface assembly of cobalt species for simultaneous acceleration of interfacial charge separation and catalytic reactions on Cd_(0.9)Zn_(0.1)S photocatalyst

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.

Enhanced charge separation by incomplete calcination modified co-doped TiO_(2)nanoparticle for isothiazolinone photocatalytic degradation

Photocatalytic oxidation techniques are promising for degradation of the highly ecotoxic and refractory isothiazolinone bactericides in relevant industrial wastewaters.However,low charge separation and directional transport efficiency under solar light radiation restrain their practical application.Here,we report a nanostructured photocatalyst doped with Gd and B in TiO_(2)with carbon incorporation and defect formation through incomplete calcination.The specific surface area,grain size,and hydrophilicity of TiO_(2)are improved,which is beneficial for the interfacial reaction between the photocatalyst and pollutants.The reduction of the bandgap,the broadening of the photo-absorption range,and the retarded electron-hole recombination promote the photocatalytic performance due to the improved oxygen vacancies based on the electron distribution modification.The difference in partial density of states(ΔPDOS)between the current catalyst and raw TiO_(2)indicates that the co-doping of Gd and B with incomplete calcination changes the electronic hybridization of conduction band and valence band near the Fermi level,and affects the band gap energy.It improved charge separation and directional transport efficiency and benefited the formation of main active species,including•OH and O_(2)•−,for the pollutant decomposition.The rate of photocatalytic removal of benzisothiazolinone(BIT)by the current photocatalyst reaches 1.25 h^(−1),being 4.31 times that of TiO_(2).The current work offers a constructive approach to the design and synthesis of nanostructured photocatalysts for the photocatalytic degradation of refractory organic pollutants.

Polarization engineering in porous organic polymers for charge separation efficiency and its applications in photocatalytic aerobic oxidations

Photocatalytic aerobic oxidation reactions are largely governed by the efficiency of charge separation and subsequent reactive oxygen species(ROS) generation. Herein, we report a polarization engineering strategy to promote the charge separation and ROS generation efficiency by substituting the benzene unit with furan/thiophene in porous organic polymers(POPs). Benefiting from the extent of local polarization, the thiophene-containing POP(JNU-218) exhibits the best photocatalytic performance in aerobic oxidation reactions, with a yield much higher than those for the furan-containing POP(JNU-217) and the benzenecontaining POP(JNU-216). Experimental studies and theoretical calculations reveal that the increase of local polarization can indeed reduce the exciton binding energy, and therefore facilitate the separation of electron-hole pairs. This work demonstrates a viable strategy to tune charge separation and ROS generation efficiency by modulating the dipole moments of the building blocks in porous polymeric organic semiconductors.

Boosting charge separation of BiVO_(4)photoanode modified with 2D metal-organic frameworks nanosheets for high-performance photoelectrochemical water splitting

Water splitting by photoelectrochemical(PEC)processes to convert solar energy into hydrogen energy using semiconductors is regarded as one of the most ideal methods to solve the current energy crisis and has attracted widespread attention.Herein,Co-based metal-organic framework(Co(bpdc)(H_(2)O)_(4)(CoMOF)nanosheets as passivation layers were in-situ constructed on the surface of Bi VO_(4)films through an uncomplicated hydrothermal method(Co-MOF/Bi VO_(4)).Under AM 1.5G illumination,synthesized CoMOF/BiVO_(4)electrode exhibited a 4-fold higher photocurrent than bare Bi VO_(4),measuring 6.0 m A/cm^(2)at 1.23 V vs.RHE in 1 mol/L potassium borate electrolyte(pH 9.5)solution.Moreover,the Co-MOF/BiVO_(4)film demonstrated a 96%charge separation efficiency,a result caused by an inhibited recombination rate of photogenerated electrons and holes by the addition of Co-MOF nanosheets.This work provides an idea for depositing inexpensive 2D Co-MOF nanosheets on the photoanode as an excellent passivation layer for solar fuel production.

Tailoring morphology symmetry of bismuth vanadate photocatalysts for efficient charge separation

Although spatial charge separation between different facets of semiconductor crystals has been recognized as a general strategy in photocatalysis, the vital role of crystal morphology symmetry in charge separation properties still remains elusive. Herein,taking monoclinic bismuth vanadate(BiVO_(4)) as a platform, we found distinct charge separation difference via rationally tailoring the morphology symmetry from octahedral to truncated octahedral crystals. For octahedral BiVO_(4), photogenerated electrons and holes can be separated between edges and quasi-equivalent facets. However, as for truncated octahedral crystals,photogenerated electrons tend to transfer to {010} facets while photogenerated holes prefer to accumulate on {120} facets, thus realizing the spatial separation of photogenerated charge between different facets. Morphology tailoring of BiVO_(4) crystals leads to a significantly improved photogenerated charge separation efficiency and photocatalytic water oxidation activity. The built-in electric field for driving the separation of photogenerated electrons and holes is considered to be modulated by tuning the morphology symmetry of BiVO_(4) crystals. This work discloses the significant roles of morphology symmetry in photogenerated charge separation and facilitates the rational design of artificial photocatalysts.