Chalcogenide-based S-scheme heterojunction photocatalysts

The unique photocatalytic mechanism of S-scheme heterojunction can be used to study new and efficient photocatalysts.By carefully selecting semiconductors for S-scheme heterojunction photocatalysts,it is possible to reduce the rate of photogenerated carrier recombination and increase the conversion efficiency of light into energy.Chalcogenides are a group of compounds that include sulfides and selenides(e.g.,CdS,ZnS,Bi_(2)S_(3),MoS_(2),ZnSe,CdSe,and CuSe).Chalcogenides have attracted considerable attention as heterojunction photocatalysts owing to their narrow bandgap,wide light absorption range,and excellent photoreduction properties.This paper presents a thorough analysis of S-scheme heterojunction photocatalysts based on chalcogenides.Following an introduction to the fundamental characteristics and benefits of S-scheme heterojunction photocatalysts,various chalcogenide-based S-scheme heterojunction photocatalyst synthesis techniques are summarized.These photocatalysts are used in numerous significant photocatalytic reactions,in-cluding the reduction of carbon dioxide,synthesis of hydrogen peroxide,conversion of organic matter,generation of hydrogen from water,nitrogen fixation,degradation of organic pollutants,and sterilization.In addition,cutting-edge characterization techniques,including in situ characterization techniques,are discussed to validate the steady and transient states of photocatalysts with an S-scheme heterojunction.Finally,the design and challenges of chalcogenide-based S-scheme heterojunction photocatalysts are explored and recommended in light of state-of-the-art research.

Enhancing Photocatalytic Hydrogen Evolution through Electronic Structure and Wettability Adjustment of ZnIn_(2)S_(4)/Bi_(2)O_(3) S-Scheme Heterojunction

The production of renewable fuels through water splitting via photocatalytic hydrogen production holds significant promise.Nonetheless,the sluggish kinetics of hydrogen evolution and the inadequate water adsorption on photocatalysts present notable challenges.In this study,we have devised a straightforward hydrothermal method to synthesize Bi_(2)O_(3)(BO)derived from metal‐organic frameworks(MOFs),loaded with flower-like ZnIn_(2)S_(4)(ZIS).This approach substantially enhances water adsorption and surface catalytic reactions,resulting in a remarkable enhancement of photocatalytic activity.By employing triethanolamine(TEOA)as a sacrificial agent,the hydrogen evolution rate achieved with 15%(mass fraction)ZIS loading on BO reached an impressive value of 1610μmol∙h^(−1)∙g^(−1),marking a 6.34-fold increase compared to that observed for bare BO.Furthermore,through density functional theory(DFT)and ab initio molecular dynamics(AIMD)calculations,we have identified the reactions occurring at the ZIS/BO S-scheme heterojunction interface,including the identification of active sites for water adsorption and catalytic reactions.This study provides valuable insights into the development of high-performance composite photocatalytic materials with tailored electronic properties and wettability.

Rational construction of CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S S-scheme heterojunction photocatalyst for extraordinary photothermal-assisted photocatalytic H_(2) evolution

Rational design of photocatalyst to maximize the use of sunlight is one of the issues to be solved in photocatalysis technology.In this study,the CuFe_(2)O_(4)@C/Cd_(0.9)Zn_(0.1)S(CFO@C/CZS)S-scheme photocatalyst with photothermal effect was synthesized by ultrasonic self-assembly combined with calcination.The dark CFO@C absorbed visible light and partly converted into heat to promote the hydrogen evolution reaction.The presence of heterojunctions inhibited the photogenerated electron-hole recombination.The graphite-carbon layer provided a stable channel for electron transfer,and the presence of magnetic CFO made recycle easier.Under the action of photothermal assistance and heterojunction,the hydrogen evolution rate of the optimal CFO@C/CZS was 80.79 mmol g^(-1) h^(-1),which was 2.55 times and 260.61 times of that of pure CZS and CFO@C,respectively.Notably,the composite samples also exhibit excellent stability and a wide range of environmental adaptability.Through experimental tests and first-principles simulation calculation methods,the plausible mechanism of photoactivity enhancement was proposed.This work provided a feasible strategy of photothermal assistance for the development of heterojunction photocatalysts with distinctive hydrogen evolution.

Rational Design and Construction of a CdS QDs/lnVO_(4) Atomic-Layer(110)/(110)Facet S-Scheme Heterojunction for Highly Efficient Photocatalytic Degradation of C_(2)H_(4)

Exploring high efficiency S-scheme heterojunction photocatalysts with strong redox ability for removing volatile organic compounds from the air is of great interest and importance.However,how to predict and regulate the transport of photogenerated carriers in heterojunctions is a great challenge.Here,density functional theory calculations were first used to successfully predict the formation of a CdS quantum dots/InVO_(4)atomic-layer(110)/(110)facet S-scheme heterojunction.Subsequently,a CdS quantum dots/InVO_(4)atomic-layer was synthesized by in-situ loading of CdS quantum dots with(110)facets onto the(110)facets of InVO_(4)atomic-layer.As a result of the deliberately constructed built-in electric field between the adjoining facets,we obtain a remarkably enhanced photocatalytic degradation rate for ethylene.This rate is 13.8 times that of pure CdS and 13.2 times that of pure InVO_(4).In-situ irradiated X-ray photoelectron spectroscopy,photoluminescence and time-resolved photoluminescence measurements were carried out.These experiments validate that the built-in electric field enhanced the dissociation of photoexcited excitons and the separation of free charge carriers,and results in the formation of S-scheme charge transfer pathways.The reaction mechanism of the photocatalytic C_(2)H_(4)oxidation is investigated by in-situ electron paramagnetic resonance.This work provides a mechanistic insight into the construction and optimization of semiconductor heterojunction photocatalysts for application to environmental remediation.

Amplified internal electric field of Cs_(2)CuBr_(4)@WO_(3-x)S-scheme heterojunction for efficient CO_(2)photoreduction

Heterojunction construction,especially S-scheme heterojunction,represents an efficient universal strategy to achieve high-performance photocatalytic materials.For further performance stimulation of these well-designed heterojunctions,modulating the interfacial internal electric field(IEF)to steer dynamic charge transfer represents a promising approach.Herein,we realized the precise regulation of Fermi level(E_(F))of the oxidation semiconductor(mesoporous WO_(3-x))by tailoring the concentration of oxygen vacancies(V_(O)),maximizing the IEF intensity in Cs_(2)CuBr_(4)@WO_(3-x)(CCB@WO_(3-x))S-scheme heterojunction.The augmented IEF affords a robust driving force for directional electron delivery,leading to boosted charge separation.Hence,the developed CCB@WO_(3-x)S-scheme heterojunction demonstrated outstanding photocatalytic CO_(2)reduction performance,with the electron consumption rate(Relectron)up to 390.34μmol g^(-1)h^(-1),which is 3.28 folds higher than that of pure CCB.An in-depth analysis of the S-scheme electron transfer mode was presented via theoretical investigations,electron spin resonance(ESR),photo-irradiated Kelvin probe force microscopy(KPFM),and in-situ X-ray photoelectron spectroscopy(XPS).Finally,the CO_(2)photoconversion route was explored in detail using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and DFT theoretical calculations.

Vacancy engineering mediated hollow structured ZnO/ZnS S-scheme heterojunction for highly efficient photocatalytic H_(2) production

Designing a step-scheme(S-scheme)heterojunction photocatalyst with vacancy engineering is a reliable approach to achieve highly efficient photocatalytic H_(2)production activity.Herein,a hollow ZnO/ZnS S-scheme heterojunction with O and Zn vacancies(VO,Zn-ZnO/ZnS)is rationally constructed via ion-exchange and calcination treatments.In such a photocatalytic system,the hollow structure combined with the introduction of dual vacancies endows the adequate light absorption.Moreover,the O and Zn vacancies serve as the trapping sites for photo-induced electrons and holes,respectively,which are beneficial for promoting the photo-induced carrier separation.Meanwhile,the S-scheme charge transfer mechanism can not only improve the separation and transfer efficiencies of photo-induced carrier but also retain the strong redox capacity.As expected,the optimized VO,Zn-ZnO/ZnS heterojunction exhibits a superior photocatalytic H_(2) production rate of 160.91 mmol g^(-1)h^(-1),approximately 643.6 times and 214.5 times with respect to that obtained on pure ZnO and ZnS,respectively.Simultaneously,the experimental results and density functional theory calculations disclose that the photo-induced carrier transfer pathway follows the S-scheme heterojunction mechanism and the introduction of O and Zn vacancies reduces the surface reaction barrier.This work provides an innovative strategy of vacancy engineering in S-scheme heterojunction for solar-to-fuel energy conversion.

Investigating the charge transfer mechanism of ZnSe QD/COF S-scheme photocatalyst for H_(2)O_(2) production by using femtosecond transient absorption spectroscopy

Hydrogen peroxide(H_(2)O_(2))has gained widespread attention as a versatile oxidant and a mild disin-fectant.Here,an electrostatic self-assembly method is applied to couple ZnSe quantum dots(QDs)with a flower-like covalent organic framework(COF)to form a step-scheme(S-scheme)photocata-lyst for H_(2)O_(2)production.The as-prepared S-scheme photocatalyst exhibits a broad light absorption range with an edge at 810 nm owing to the synergistic effect between the ZnSe QDs and COF.The S-scheme charge-carrier transfer mechanism is validated by performing Fermi level calculations and in-situ X-ray photoelectron and femtosecond transient absorption spectroscopies.Photolumi-nescence,time-resolved photoluminescence,photocurrent response,electrochemical impedance spectroscopy,and electron paramagnetic resonance results show that the S-scheme heterojunction not only promotes charge carrier separation but also boosts the redox ability,resulting in enhanced photocatalytic performance.Remarkably,a 10%-ZnSe QD/COF has excellent photocatalytic H_(2)O_(2)-production activity,and the optimal S-scheme composite with ethanol as the hole scavenger yields a H_(2)O_(2)-production rate of 1895 mol g^(-1)h^(-1).This study presents an example of a high-performance organic/inorganic S-scheme photocatalyst for H_(2)O_(2)production.

Molten salt construction of core-shell structured S-scheme CuInS_(2)@CoS_(2) heterojunction to boost charge transfer for efficient photocatalytic CO_(2) reduction

Weak redox ability and severe charge recombination pose significant obstacles to the advancement of CO_(2) photoreduction.To tackle this challenge and enhance the CO_(2) photoconversion efficiency,fabricating well-matched S-scheme heterostructure and establishing a robust built-in electric field emerge as pivotal strategies.In pursuit of this goal,a core-shell structured CuInS_(2)@CoS_(2)S-scheme heterojunction was meticulously engineered through a two-step molten salt method.This approach over the CuInS_(2)-based composites produced an internal electric field owing to the disparity be-tween the Fermi levels of CoS_(2) and CuInS_(2) at their interface.Consequently,the electric field facili-tated the directed migration of charges and the proficient separation of photoinduced carriers.The resulting CuInS_(2)@CoS_(2) heterostructure exhibited remarkable CO_(2) photoreduction performance,which was 21.7 and 26.5 times that of pure CuInS_(2) and CoS_(2),respectively.The S-scheme heterojunc-tion photogenerated charge transfer mechanism was validated through a series of rigorous anal-yses,including in situ irradiation X-ray photoelectron spectroscopy,work function calculations,and differential charge density examinations.Furthermore,in situ infrared spectroscopy and density functional theory calculations corroborated the fact that the CuInS_(2)@CoS_(2) heterojunction substan-tially lowered the formation energy of *COOH and *CO.This study demonstrates the application potential of S-scheme heterojunctions fabricated via the molten salt method in the realm of ad-dressing carbon-related environmental issues.

Self-assembled S-scheme In_(2.77)S_(4)/K^(+)-doped g-C_(3)N_(4)photocatalyst with selective O_(2) reduction pathway for efficient H_(2)O_(2) production using water and air

The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.

NiMoO_(4)/ZnIn_(2)S_(4)S-scheme异质结的制备及光催化产氢性能增强机制

首先通过水热法制备得到NiMoO_(4)·x H_(2)O前驱体,再经高温煅烧得到NiMoO_(4)纳米棒,最后通过超声混合及溶剂蒸干处理将NiMoO_(4)与ZnIn_(2)S_(4)复合构建了NiMoO_(4)/ZnIn_(2)S_(4)S-scheme异质结光催化剂。研究结果表明,NiMoO_(4)质量分数为10.7%时,复合材料(10.7-NiMoO_(4)/ZnIn_(2)S_(4))具有较好的载流子分离效率,较低的界面电荷转移阻力和较大的电化学活性面积。在300 W氙灯照射下,其产氢速率可达29.04 mmol·g^(-1)·h^(-1),约为单体ZnIn_(2)S_(4)(5.58 mmol·g^(-1)·h^(-1))的5.20倍。自由基捕获实验及能带结构分析表明,NiMoO_(4)和ZnIn_(2)S_(4)之间形成了S-scheme电荷转移机制,不仅促进了载流子的分离与迁移,而且保留了较强的氧化还原能力。此外,NiMoO_(4)的引入提高了异质结的电化学活性面积,以上因素协同提高了体系的光催化析氢性能。

将In_(2)O_(3)/CdSe-DETA纳米复合材料中的电荷转移从Type-Ⅰ转变为S-Scheme以提高光催化制氢的活性和稳定性

化石能源的问题限制了人类的发展。解决这个问题的有效方法是发展可持续性的清洁能源。近年来,氢气作为一种新型的清洁能源被争相报道。氢气燃烧热很大,且产物只有水,完全符合绿色环保可持续性能源的特点。因此,解决氢能源的生产方法就可以有效地解决能源危机问题。自TiO_(2)在1972年作为光催化剂分解水产生氢气开始,半导体光催化剂分解水产生氢气登上了历史的舞台。然而,单一组分光催化剂的固有缺点限制了它的实际应用,寻找克服单一组分光催化剂缺点的解决方案仍然具有挑战性。相对于单一的光催化剂,复合材料光催化剂可以更有效地分离光生电子和空穴,增加光催化析氢反应的速率。因此,通过选择复合材料异质结处合适的光催化机制(如:S-scheme),可以进一步提升催化剂的光催化析氢活性和稳定性。本文通过改变合成条件获得了一系列具有不同带隙宽度的单一CdSe-DETA光催化剂。光催化实验显示调节CdSe-DETA的带隙(2.31eV)可以获得最佳的光催化产氢活性,但是其稳定性很差。因此,我们将CdSe-DETA纳米花附着在In2O3多孔纳米片表面,构建了In_(2)O_(3)/CdSe-DETA纳米复合材料,以提升光催化析氢活性,稳定性和光电流响应。In_(2)O_(3)/CdSe-DETA纳米复合材料中异质结的类型可随着CdSe-DETA带隙宽度的改变而变化。随着CdSe-DETA带隙宽度的增加,异质结的类型可从Type-I型转变到S-scheme型。相对于单一光催化剂和Type-I型光催化剂,S-scheme型In_(2)O_(3)/CdSe-DETA纳米复合材料具有更高的光催化活性以及良好的稳定性。因此,我们选择S-scheme异质结的In_(2)O_(3)/CdSe-DETA纳米复合材料来获得光催化活性和稳定性的最大收益。此外,我们通过差分电荷密度计算结合实验结果证实了S-scheme异质结的存在。S-scheme异质结In_(2)O_(3)/CdSe-DETA纳米复合材料有效分离了光生电子和空穴,最大程度地利用复合材料的导带和价带,高效且稳定的光催化析氢。本研究展示了一种调制载流子转移机制的策略,可为开发高效的析氢光催化剂提供借鉴。

Fabrication of g-C_(3)N_(4) nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)nanocomposites:Double S-scheme photocatalysts with impressive performance for the removal of antibiotics under visible light

Novel graphitic carbon nitride(g-C_(3)N_(4))nanosheet/Bi_(5)O_(7)Br/NH_(2)-MIL-88B(Fe)photocatalysts(denoted as GCN-NSh/Bi_(5)O_(7)Br/FeMOF,in which MOF is metal–organic framework)with double S-scheme heterojunctions were synthesized by a facile solvothermal route.The resultant materials were examined by X-ray photoelectron spectrometer(XPS),X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive X-ray spectroscopy(EDX),transmission electron microscopy(TEM),high-resolution transmission electron microscopy(HRTEM),photoluminescence spectroscopy(PL),Fourier transform infrared spectroscopy(FT-IR),UV-Vis diffuse reflection spectroscopy(UV-vis DRS),photocurrent density,electrochemical impedance spectroscopy(EIS),and Brunauer–Emmett–Teller(BET)analyses.After the integration of Fe-MOF with GCN-NSh/Bi_(5)O_(7)Br,the removal constant of tetracycline over the optimal GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite was promoted 33 times compared with that of the pristine GCN.The GCN-NSh/Bi_(5)O_(7)Br/Fe-MOF(15wt%)nanocomposite showed superior photoactivity to azithromycin,metronidazole,and cephalexin removal that was 36.4,20.2,and 14.6 times higher than that of pure GCN,respectively.Radical quenching tests showed that·O_(2)-and h+mainly contributed to the elimination reaction.In addition,the nanocomposite maintained excellent activity after 4 successive cycles.Based on the developed n–n heterojunctions among n-GCN-NSh,n-Bi_(5)O_(7)Br,and n-Fe-MOF semiconductors,the double S-scheme charge transfer mechanism was proposed for the destruction of the selected antibiotics.

S-Scheme异质结光催化产氢研究进展

随着不可再生能源的大量消耗,能源短缺成为人类社会面临的重大挑战。在众多新能源制备技术中,光催化分解水制氢技术只需丰富的太阳能作为驱动力就可以实现分解水制氢,且制氢条件温和、绿色无污染,被认为是解决当前能源短缺危机的有效技术之一。光催化制氢技术的核心是光催化剂,因此发展高效稳定的光催化剂至关重要。然而,单组分光催化剂由于空穴-电子复合速度快、氧化还原能力有限、太阳能利用效率低等原因,通常只能呈现出有限的光催化分解水制氢活性。为此,科研人员做了大量改性研究,其中常见的改性策略有元素掺杂、助催化剂修饰、构建异质结等。通常,元素掺杂、助催化剂修饰等改性手段可以在一定程度上提高光催化剂的制氢活性,但并不能有效解决单相光催化剂的缺陷,导致其改性效果受到制约。然而,在两个或多个半导体之间构建异质结可以有效解决上述单组分光催化剂的缺陷。相较于当前流行的传统II型异质结和Z-型异质结,S-型异质结的电荷转移机制更为合理,受到科学家们的广泛关注与应用。因此,本文首先对S-型异质结光催化体系的发展背景进行介绍,包括传统II型异质结、全固态Z-型异质结和液相Z-型异质结光催化系统。随后对S-型异质结光催化机理进行具体阐述,并对其机理表征方法进行了概述,包括原位XPS光谱、开尔文探针力显微镜、电子顺磁共振、选择性沉积和密度泛函理论计算。此外,本文系统总结了当前报道的S-型异质结光催化剂在分解水制氢领域中的应用及其制氢性能增强机理分析,包括g-C_(3)N_(4)基、金属硫化物基、TiO_(2)基、其他氧化物基等S型异质结光催化剂。总体而言,S型异质结光催化剂由于其有效的载流子分离和增强的光氧化还原能力,通常呈现出优异的光催化制氢性能。最后,指出了S型异质结光催化剂在分解水产氢中的发展瓶颈,并展望攻克该瓶颈以进一步提高S型异质结的光催化效率,从而达到工业应用标准。

S-scheme ZnO/MoS_(2)异质结构筑与对盐酸四环素降解性能

抗生素药物使用范围广且用量大,导致大量抗生素废水进入水体或者残留在土壤环境中,对人类健康造成威胁,然而传统工艺对其去除效果并不理想.以ZnO为基底,通过掺杂MoS_(2),制备了S-scheme ZnO/MoS_(2)异质结复合材料,研究了该材料对抗生素废水的净化性能.通过调节复合材料中ZnO含量、光照条件、盐酸四环素浓度等,探讨了ZnO/MoS_(2)复合材料对不同浓度盐酸四环素(tetracycline hydrochloride,TC)废水的净化效果.结果表明:在光照条件下,催化剂复合比为1∶1的ZnO/MoS_(2)复合材料对60 mg·L^(-1)四环素废水的降解效率可达88%(pH=7,105 min);电子传递与污染物降解机理研究表明,电子由ZnO导带迁移至MoS_(2)价带,形成S-scheme异质结,从而有效提高了催化效率与污染物降解性能.

S-scheme光催化剂在制氢、还原CO_(2)及降解污染物领域的研究进展

简要阐述了S-scheme光催化剂的反应机理,综述了多种由不同材料构建而成的S-scheme光催化剂在光分解水制氢、CO_(2)还原及污染物降解等领域的应用研究进展,简要分析了S-scheme光催化剂光催化效率高的主要原因,并对S-scheme光催化剂未来研究方向与应用前景进行了展望。

Sulfur-doped g-C3N4/TiO2 S-scheme heterojunction photocatalyst for Congo Red photodegradation

Constructing step-scheme(S-scheme)heterojunctions has been confirmed as a promising strategy for enhancing the photocatalytic activity of composite materials.In this work,a series of sulfur-doped g-C3N4(SCN)/TiO2 S-scheme photocatalysts were synthesized using electrospinning and calcination methods.The as-prepared SCN/TiO2 composites showed superior photocatalytic performance than pure TiO2 and SCN in the photocatalytic degradation of Congo Red(CR)aqueous solution.The significant enhancement in photocatalytic activity benefited not only from the 1D well-distributed nanostructure,but also from the S-scheme heterojunction.Furthermore,the XPS analyses and DFT calculations demonstrated that electrons were transferred from SCN to TiO2 across the interface of the SCN/TiO2 composites.The built-in electric field,band edge bending,and Coulomb interaction synergistically facilitated the recombination of relatively useless electrons and holes in hybrid when the interface was irradiated by simulated solar light.Therefore,the remaining electrons and holes with higher reducibility and oxidizability endowed the composite with supreme redox ability.These results were adequately verified by radical trapping experiments,ESR tests,and in situ XPS analyses,suggesting that the electron immigration in the photocatalyst followed the S-scheme heterojunction mechanism.This work can enrich our knowledge of the design and fabrication of novel S-scheme heterojunction photocatalysts and provide a promising strategy for solving environmental pollution in the future.

Bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalysts toward artificial carbon cycling

Although both the aerobic photocatalytic oxidation of organic pollutants into CO2 and the anaerobic photocatalytic reduction of CO2 into solar fuels have been intensively studied,few efforts have been devoted to combining these carbon-involved photocatalytic oxidation-reduction processes together,by which an artificial photocatalytic carbon cycling process can be established.The key challenge lies in the exploitation of efficient bifunctional photocatalysts,capable of triggering both aerobic oxidation and anaerobic reduction reactions.In this work,a bifunctional ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst is successfully constructed,which not only demonstrates superior aerobic photocatalytic oxidation performance in degrading an organic pollutant(using the dye,Rhodamine B as a model),but also exhibits impressive photocatalytic CO2 reduction performance under anaerobic conditions.Moreover,a direct conversion of Rhodamine B to solar fuels in a one-pot anaerobic reactor can be achieved with the as-prepared ternary g-C3N4/Bi/BiVO4 hybrid photocatalyst.The excellent bifunctional photocatalytic performance of the g-C3N4/Bi/BiVO4 photocatalyst is associated with the formation of efficient S-scheme hybrid junctions,which contribute to promoting the appropriate charge dynamics,and sustaining favorable charge potentials.The formation of the S-scheme heterojunction is supported by scavenger studies and density functional theory calculations.Moreover,the in-situ formed plasmonic metallic Bi nanoparticles in the S-scheme hybrid g-C3N4/Bi/BiVO4 photocatalyst enhances vectorial interfacial electron transfer.This novel bifunctional S-scheme g-C3N4/Bi/BiVO4 hybrid photocatalyst system provides new insights for the further development of an integrated aerobic-anaerobic reaction system for photocatalytic carbon cycling.

Construction of LSPR-enhanced 0D/2D CdS/MoO3‒x S-scheme heterojunctions for visible-light-driven photocatalytic H2 evolution

Plasmonic nonmetal semiconductors with localized surface plasmon resonance(LSPR)effects possess extended light-response ranges and can act as highly efficient H2 generation photocatalysts.Herein,an LSPR-enhanced 0D/2D CdS/MoO3‒x heterojunction has been synthesized by the growth of 0D CdS nanoparticles on 2D plasmonic MoO3‒x elliptical nanosheets via a simple coprecipitation method.Taking advantage of the LSPR effect of the MoO3‒x elliptical nanosheets,the light absorption of the CdS/MoO3‒x heterojunction was extended from 600 nm to the near-infrared region(1400 nm).Furthermore,the introduction of 2D plasmonic MoO3‒x elliptical nanosheets not only provided a platform for the growth of CdS nanoparticles,but also contributed to the construction of an LSPR-enhanced S-scheme structure due to the interface between the MoO3‒x and CdS,accelerating the separation of light-induced electrons and holes.Therefore,the CdS/MoO3‒x heterojunction exhibited higher photocatalytic H2 generation activity than pristine CdS under visible light irradiation,including under 420,450,550,and 650 nm monochromic light,as well as improved photo-corrosion performance.

In situ fabrication of Bi_(2)Se_(3)/g-C_(3)N_(4)S-scheme photocatalyst with improved photocatalytic activity

Bismuth selenide(Bi_(2)Se_(3))is an attractive visible-light-responsive semiconductor that can absorb a full range of visible and near-infrared light.However,its poor redox capacity and rapid carrier recombination limit its application in photocatalytic oxidation.In this study,we adopted Bi_(2)Se_(3)as the couple part of graphitic carbon nitride(g-C_(3)N_(4))to construct a Bi_(2)Se_(3)/g-C_(3)N_(4)composite photocatalyst.Through in situ fabrication,the self-developed Bi2O3/g-C_(3)N_(4)precursor was transformed into a Bi_(2)Se_(3)/g-C_(3)N_(4)heterojunction.The as-prepared Bi_(2)Se_(3)/g-C_(3)N_(4)composite exhibited much higher visible-light-driven photocatalytic activity than pristine Bi_(2)Se_(3)and g-C_(3)N_(4)in the removal of phenol.The enhanced photocatalytic activity was ascribed to the S-scheme configuration of Bi_(2)Se_(3)/g-C_(3)N_(4);this was confirmed by the energy-level shift,photoluminescence analysis,computational structure study,and reactive-radical testing.In the S-scheme heterojunction,photo-excited electrons in the conduction band of g-C_(3)N_(4)migrate to the valence band of Bi_(2)Se_(3)and combine with the excited holes therein.By consuming less reactive carriers,the S-scheme heterojunction can not only effectively promote charge separation,but also preserve more reactive photo-generated carriers.This property enhances the photocatalytic activity.

S-scheme Sb2WO6/g-C3N4 photocatalysts with enhanced visible-light-induced photocatalytic NO oxidation performance

Normal photocatalysts cannot effectively remove low-concentration NO because of the high recombination rate of the photogenerated carriers.To overcome this problem,S-scheme composites have been developed to fabricate photocatalysts.Herein,a novel S-scheme Sb2WO6/g-C3N4 nanocomposite was fabricated by an ultrasound-assisted method,which exhibited excellent performance for photocatalytic ppb-level NO removal.Compared with the pure constituents of the nanocomposite,the as-prepared 15%-Sb2WO6/g-C3N4 photocatalyst could remove more than 68%continuous-flowing NO(initial concentration:400 ppb)under visible-light irradiation in 30 min.The findings of the trapping experiments confirmed that•O2^–and h+were the important active species in the NO oxidation reaction.Meanwhile,the transient photocurrent response and PL spectroscopy analyses proved that the unique S-scheme structure of the samples could enhance the charge separation efficiency.In situ DRIFTS revealed that the photocatalytic reaction pathway of NO removal over the Sb2WO6/g-C3N4 nanocomposite occurred via an oxygen-induced route.The present work proposes a new concept for fabricating efficient photocatalysts for photocatalytic ppb-level NO oxidation and provides deeper insights into the mechanism of photocatalytic NO oxidation.