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.

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.

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.

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.

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.

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.

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.

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.

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 O2•−,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.

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.

Enhanced charge separation by continuous homojunction with spatially separated redox sites for hydrogen evolution

Photocatalytic hydrogen generation represents a promising strategy for the establishment of a sustainable and environmentally friendly energy reservoir.However,the current solar-to-hydrogen conversion efficiency is not yet sufficient for practical hydrogen production,highlighting the need for further research and development.Here,we report the synthesis of a Sn-doped TiO_(2)continuous homojunction hollow sphere,achieved through controlled calcination time.The incorporation of a gradient doping profile has been demonstrated to generate a gradient in the band edge energy,facilitating carrier orientation migration.Furthermore,the hollow sphere’s outer and inner sides provide spatially separated reaction sites allowing for the separate acceptance of holes and electrons,which enables the rapid utilization of carriers after separation.As a result,the hollow sphere TiO_(2)with gradient Sn doping exhibits a significantly increased hydrogen production rate of 20.1 mmol·g^(−1)·h^(−1).This study offers a compelling and effective approach to the designing and fabricating highly efficient nanostructured photocatalysts for solar energy conversion applications.

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.

Construction of charge transfer chain in Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)composites to accelerate photogenerated charge separation

Photogenerated charge separation and transfer is one of the bottleneck steps in photocatalysis,and efficient charge separation strategies are strongly desired.Here,mimicking the electron transport chain in natural photosynthesis,we report the design and fabrication of a charge transfer chain using bismuth-based semiconductor as a proof-of-concept.In view of the thermodynamic energy band positions and structural similarity based on the density functional theory(DFT)analysis,heterostructured combination ofα-Bi_(2)O_(3),perovskite-like Bi_(4)Ti_(3)O_(12),and sillenite Bi12TiO20 was designed for fabrication of charge transfer chain.By tuning the molar ratio of Bi and Ti precursors,the Bi_(4)Ti_(3)O_(12)and Bi12TiO20 particles were formed on the surface ofα-Bi_(2)O_(3)by an insitu transformation process,giving rise to Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)composites with charge transfer chain.We propose that the effective charge transfer is accomplished amongα-Bi_(2)O_(3),Bi12TiO20,and Bi_(4)Ti_(3)O_(12),which significantly improves the photogenerated charge separation and transfer,as indicated by photoluminescene,time-resolved photoluminescene,and electrochemical impedance spectra results.As expected,the Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)shows the superior photocatalytic activity for the degradation of environmental pollutants with high concentration.Even for the refractory pollutants like 4-chlorophenol,the optimal Bi_(12)TiO_(20)-Bi_(4)Ti_(3)O_(12)/α-Bi_(2)O_(3)composite shows 28 times higher than that ofα-Bi_(2)O_(3)for photocatalytic degradation,verifying the superiority of photogenerated charge transfer chain in photocatalysis.This work demonstrates the feasibility of the charge transfer chain strategy to boost the photogenerated charge separation,which is of great significance for designing energy and environmental-related materials in heterogonous photocatalysis.

Interface charge separation in Cu_(2)CoSnS_(4)/ZnIn_(2)S_(4) heterojunction for boosting photocatalytic hydrogen production

The practical application of hexagonal ZnIn_(2)S_(4)(ZIS)as a visible-light photocatalyst for hydrogen(H_(2))production is hindered by rapid internal charge recombination.In this study,we successfully synthesized Cu_(2)CoSnS_(4)(CCTS)nanocrystals and loaded them onto the surface of ZIS nanosheets to create a p-n heterojunction photocatalyst.The optimized Cu_(2)CoSnS_(4)/ZnIn_(2)S_(4)(CCTS/ZIS)heterojunction exhibited a significantly higher visible-light photo-catalytic H_(2)evolution rate of 4.90 mmol·g^(-1)·h^(-1)compared to ZIS and CCTS alone.The enhanced photocatalytic efficiency was attributed to improved electron transfer and charge separation at the heterojunction interface.The formation of p-n heterojunction facilitated the accumulation of valence band electrons in ZIS and conduction band holes in CCTS,effectively suppressing the recombination of photogenerated electrons and holes.Theoretical calculations,spectroscopic,and photoelectrochemical characterizations supported the findings.This work pre-sents a promising approach for designing efficient p-n heterojunction semiconductor photocatalysts for practical applications in visible-light-driven hydrogen evolution.

Nanoporous MoO_(3−x)/BiVO_(4)photoanodes promoting charge separation for efficient photoelectrochemical water splitting

Owing to the relatively short hole diffusion length,severe charge recombination in the bulk of bismuth vanadate(BiVO_(4))is the key issue for photoelectrochemical water splitting.Herein,we design a nanoporous MoO_(3−x)/BiVO_(4)heterojunction photoanode to promote charge separation.The efficient electron transport properties of oxygen deficient MoO_(3−x)and the nanoporous structure are beneficial for charge separation,leading to a significantly enhanced PEC performance.The optimized MoO_(3−x)/BiVO_(4)heterojunction photoanode exhibits a photocurrent density of 5.07 mA·cm^(−2)for Na_(2)SO_(3)oxidation.By depositing FeOOH/NiOOH dual oxygen evolution cocatalysts to promote surface kinetics,a high photocurrent density of 4.81 mA·cm^(−2)can be achieved for PEC water splitting,exhibiting an excellent applied bias photon-to-current efficiency of 1.57%.Moreover,stable overall water splitting is achieved under consecutive light illumination for 10 h.We provide a proof of concept for the design of efficient BiVO_(4)-based heterojunction photoanodes for stable PEC water splitting.

A carbon-rich g-C_(3)N_(4) with promoted charge separation for highly efficient photocatalytic degradation of amoxicillin

A novel carbon-rich g-C_(3)N_(4) nanosheets with large surface area was prepared by facile thermal polymerization method using urea and 1,3,5-cyclohexanetriol.Plenty of carbon-rich functional groups were introduced into the surface layers of g-C_(3)N_(4),which constructed the built-in electric field(BIEF)and resulted in improved charge separation;therefore,the carbon-rich g-C_(3)N_(4) displayed superior photocatalytic activity for amoxicillin degradation under solar light.The contaminant degradation mechanism was proposed based on radical quenching experiments,intermediates analysis and density functional theory(DFT)calculation.Moreover,the reusing experiments showed the high stability of the material,and the amoxicillin degradation under various water matrix parameters indicated its high applicability on pollutants treatment,all of which demonstrated its high engineering application potentials.

Impact of the Vertical Velocity Field on Charging Processes and Charge Separation in a Simulated Thunderstorm

A three-dimensional（3D） charging-discharging cloud resolution model was used to investigate the impact of the vertical velocity field on the charging processes and the formation of charge structure in a strong thunderstorm. The distribution and evolution of ice particle content and charges on ice particles were analyzed in different vertical velocity fields. The results show that the ice particles in the vertical velocity range from 1 to 5 m s-1obtained the most charge through charging processes during the lifetime of the thunderstorm. The magnitude of the charges could reach 1014 n C. Before the beginning of lightning activity,the charges produced in updraft region 2（updraft speed 13 m s-1） and updraft region 1（updraft speed between 5 and 13 m s-1） were relatively significant. The magnitudes of charge reached 1013 n C, which clearly impacted upon the early lightning activity. The vertical velocity conditions in the quasi-steady region（updraft speed between -1 and 1 m s-1） were the most conducive for charge separation on ice particles on different scales. Accordingly, a net charge structure always appeared in the quasi-steady and adjacent regions. Based on the results, a conceptual model of ice particle charging, charge separation, and charge structure formation in the flow field was constructed. The model helps to explain observations of the＂lightning hole＂ phenomenon.

Achieving simultaneous Cu particles anchoring in meso-porous TiO_(2) nanofabrication for enhancing photo-catalytic CO_(2) reduction through rapid charge separation

A facile solvo-thermal approach was successfully employed to prepare titanium oxide (TiO_(2)) nano-aggregates with simultaneous copper particles anchoring. The as-synthesized composite could convert CO_(2) into CH_(4) and CO products under simulated solar irradiation. The impact of copper loading amounts on the photo-reduction capability was evaluated. It was found proper amount of Cu loading could enhance the activity of CO_(2) photo-reduction. As a result, the optimal composite (TiO_(2)^(-)Cu-5%) consisting of TiO_(2) supported with 5% (mole ratio) Cu exhibits 2.2 times higher CH_(4) yield and 3 times higher CO yield compared with pure TiO_(2). Conduction band calculated from the band gap and valence X-ray photoelectron spectroscopy (XPS) indicated TiO_(2) nano-aggregates have suitable band edge alignment with respect to the CO_(2)/CH_(4) and CO_(2)/CO redox potential. Furthermore, with involving of Cu particles, an efficient separation of photo-generated charges was achieved on the basis of photocurrent response and photoluminescence spectra results, which contributed to the improved photo-catalytic performance. The present work suggested that the Cu-decorated TiO_(2) could serve as an efficient photo-catalyst for solar-driven CO_(2) photo-reduction.

Impact of surface hydroxylation in MgO-/SnO-nanocluster modified TiO_2 anatase(101) composites on visible light absorption, charge separation and reducibility

Surface modification with metal oxide nanoclusters has emerged as a candidate for the enhancement of the photocatalytic activity of titanium dioxide. An increase in visible light absorption and the suppression of charge carrier recombination are necessary to improve the efficiency. We have studied Mg4O4 and Sn4O4 nanoclusters modifying the（101） surface of anatase TiO2 using density functional theory corrected for on-site Coulomb interactions（DFT ＋ U）. Such studies typically focus on the pristine surface, free of the point defects and surface hydroxyls present in real surfaces. We have also examined the impact of partial hydroxylation of the anatase surface on a variety of outcomes such as nanocluster adsorption, light absorption, charge separation and reducibility. Our results indicate that the modifiers adsorb strongly at the surface, irrespective of the presence of hydroxyl groups, and that modification extends light absorption into the visible range while enhancing UV activity. Our model for the excited state of the heterostructures demonstrates that photoexcited electrons and holes are separated onto the TiO2 surface and metal oxide nanocluster respectively. Comparisons with bare TiO2 and other TiO2-based photocatalyst materials are presented throughout.