Defect-assisted surface modification enhances the visible light photocatalytic performance of g-C_3N_4@C-TiO_2 direct Z-scheme heterojunctions

To increase the number of active sites and defects in TiO2 and promote rapid and efficient transfer of photogenerated charges, a g-C3N4@C-TiO2 composite photocatalyst was prepared via in situ deposition of g-C3N4 on a carbon-doped anatase TiO2 surface. The effects of carbon doping state and surface modification of g-C3N4 on the performance of g-C3N4@C-TiO2 composite photocatalysts were studied by X-ray diffraction, X-ray photoelectron spectroscopy, UV-visible diffuse-reflectance spectroscopy, transmission electron microscopy, electrochemical impedance spectroscopy, photoluminescence, and electron paramagnetic resonance. With increasing carbon doping content, the carbon doping state in TiO2 gradually changed from gap to substitution doping. Although the number of oxygen vacancies gradually increased, the degradation efficiency of g-C3N4@C-TiO2 for RhB (phenol) initially increased and subsequently decreased with increasing carbon content. The g-C3N4@10C-TiO2 sample exhibited the highest apparent reaction rate constant of 0.036 min儃1 (0.039 min儃1) for RhB (phenol) degradation, which was 150 (139), 6.4 (6.8), 2.3 (3), and 1.7 (2.1) times higher than that of pure TiO2, 10C-TiO2, g-C3N4, and g-C3N4@TiO2, respectively. g-C3N4 was grown in situ on the surface of C-TiO2 by surface carbon hybridization and bonding. The resultant novel g-C3N4@C-TiO2 photocatalyst exhibited direct Z-scheme heterojunctions with non-local impurity levels. The high photocatalytic activity can be attributed to the synergistic effects of the improved visible light response ability, higher photogenerated electron transfer efficiency, and redox ability arising from Z-type heterojunctions.

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

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

ZnO/CeO_(2)/carbon xerogel composites with direct Z-scheme heterojunctions:Enhancing photocatalytic remediation of 4-chlorophenol under visible light

This paper aims to create visible light driven ternary photocatalysts using zinc oxide(ZnO),cerium(IV)oxide(CeO_(2)),and carbon xerogel(CX) as constituent materials.The use of CeO_(2) is based on the creation of direct-Z-scheme heterojunctions with the ZnO and the consequent diminishing of charge recombination,whereas the carbon xerogel inclusion is predicted to minimize bandgap energy,decrease electro n-hole reco mbination,and boost specific surface area.Furthermo re,the choice of the black-wattle tannin as a carbonaceous precursor was targeted at the development of an environmentally friendly and affordable composite.The existence of the hexagonal phase of zinc oxide and cubic structure of the cerium(IV) oxide in the ternary material was confirmed by X-ray diffractometry and X-ray photoelectron spectroscopy,with the latter also suggesting chemical bonding between the ZnO and the CX due to the creation of zinc oxycarbide complexes.The inclusion of the carbon xerogel provokes a significant modification in the morphology of the ternary material,resulting in an increased surface area and smaller particle aggregates.The CX/ZnO-CeO_(2) ternary composite obtains the highest photocatalytic efficiency among all the materials studied,degrading 100% of 4-chlorophenol under simulated sunlight and 68% under visible radiation,after 5 h.The increased photocatalytic activity can be attributed to the formation of direct Z-scheme heterojunctions between the semiconductors,higher visible light response,and higher specific surface area,as evidenced by the results obtained by active radical scavenging,chronoamperometry,diffuse reflectance spectroscopy,and N_(2) adsorption-desorption isotherms.

Bifunctional noble-metal-free cocatalyst coating enabling better coupling of photocatalytic CO_(2)reduction and H_(2)O oxidation on direct Z-scheme heterojunction

Selective loading of spatially separated redox cocatalysts on direct Z-scheme heterojunctions holds great promise for advancing the efficiency of artificial photosynthesis,which however is limited to the photodeposition of noble metal cocatalysts and the fabrication of hollow double-shelled semiconductor heterojunctions.Moreover,the co-exposure of discrete cocatalyst and semiconductor increases the product diversity when both the exposed sites of which participate in CO_(2)photoreduction.Herein,we present a facile and versatile protocol to overcome these limitations via surface coating of Z-scheme heterojunctions with bifunctional noble-metal-free cocatalysts.With Cu_(2)O/Fe_(2)O_(3)(CF)as a model heterojunction and layered Ni(OH)_(2)as a model cocatalyst,it is found that Ni(OH)_(2)lying on the surfaces of Cu_(2)O and Fe_(2)O_(3)separately co-catalyzes the CO_(2)reduction and H_(2)O oxidation.Thorough experimental and theoretical investigation reveals that the Ni(OH)_(2)outer layer:(i)mitigates the charge recombination in CF and balances their transfer and consumption;(ii)reduces the rate-determining barriers for CO_(2)-to-CO and H_(2)O-to-O_(2)conversion,(iii)suppresses the side proton reduction occurring on CF,and(iv)protects the CF from component detachment.As expected,the redox reactions stoichiometrically proceed,and significantly enhanced photocatalytic activity,selectivity,and stability in CO generation are achieved by the stacked Cu_(2)O/Fe_(2)O_(3)@Ni(OH)_(2)in contrast to CF.This study demonstrates the significance of the synergy between bifunctional cocatalysts and Z-scheme heterojunctions for improving the efficacy of overall redox reactions,opening a fresh avenue for the rational design of artificial photosynthetic systems.

Energy band engineering of Bi_(2)O_(2.33)–CdS direct Z-scheme heterojunction for enhanced photocatalytic reduction of CO_(2)

In this work,a Bi_(2)O_(2.33)–CdS direct Z-scheme heterojunction was fabricated based on energy band engineering.The Bi_(2)O_(2.33)core nanoflakes were first synthesized by electrodeposition which was followed by an annealing process to fabricate this heterojunction.Then the Cd S shell was deposited on Bi_(2)O_(2.33)nanoflakes utilizing the solution method,during which a suitable concentration of Cd Clsolution was used for forming a homogeneous and continuous integrated CdS shell.A space charge region and an internal electric field from CdS(+)to Bi_(2)O_(2.33)(-),which drove a direct Z-scheme charge transfer process,were formed at the interface.The Bi_(2)O_(2.33)–CdS exhibited excellent photocatalytic performance for CO_(2)reduction mainly attributed to the satisfactory photoinduced charge separation and transport efficiency in the direct Z-scheme heterojunction.The photocatalytic CO_(2)reduction ability of Bi_(2)O_(2.33)–CdS was significantly enhanced compared with single Bi_(2)O_(2.33)or Cd S,with a CO_(2)yield rate of ca.2.9μmol/(cm^(2)h)under a 300 W Xe lamp.The reduction of CO_(2)to CO_(2)demonstrated 94.0%selectivity.

Direct electrospinning method for the construction of Z-scheme TiO_2/g-C_3N_4/RGO ternary heterojunction photocatalysts with remarkably ameliorated photocatalytic performance

A series of Z-scheme TiO2/g-C3N4/RGO ternary heterojunction photocatalysts are successfully constructed via a direct electrospinning technique coupled with an annealing process for the first time. They are investigated comprehensively in terms of crystal structure, morphology, composition, specific surface area, photoelectrochemical properties, photodegradation performance, etc. Compared with binary TiO2/g-C3N4 and single-component photocatalysts, ternary heterojunction photocatalysts show the best photodegradation performance for RhB under stimulated sunlight. This can be attributed to the enlarged specific surface area (111.41 m2/g), the formation of Z-scheme heterojunction, and the high separation migration efficiency of photoexcited charge carriers. A potential Z-scheme mechanism for ternary heterojunction photocatalysts is proposed to elucidate the remarkably ameliorated photocatalytic performance based on active species trapping experiments, PL detection test of hydroxyl radicals, and photoelectrochemical properties.

0D/3D direct Z-scheme heterojunctions hybridizing by MoS2 quantum dots and honeycomb conjugated triazine polymers (CTPs) for enhanced photocatalytic performance

Herein,a novel direct Z-scheme photocatalyst was accomplished by hybridization of 0D MoS2 quantum dots(MSQDs)and 3D honeycomb-like conjugated triazine polymers(CTP)(namely,CTP-MSQD).The unique 0D/3D hierarchical structure significantly enhanced the exposure of active sites and light harvesting property,while the formed p-n junction enabled the direct strong interface coupling without the necessity of any mediators.The optimized CTP-MSQD3 exhibited continuously increased visible-light-driven photocatalytic activity and strong durability both in Cr(VI)reduction and H2 evolution,featured a rate of 0.069 min^(-1) and 1070μmol/(hr•g),respectively,which were 8 times than those of pure 3D-CTP(0.009 min^(−1) and 129μmol/(hr•g)).We believe that this work provides a promising photocatalyst system that combines a 0D/3D hierarchical structure and a Z-scheme charge flow for efficient and stable photocatalytic conversion.

Double Z-Scheme g-C_(3)N_(4)/BiOI/CdS heterojunction with I_(3)^(-)/I^(-) pairs for enhanced visible light photocatalytic performance

The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction photocatalyst with I_(3)^(-)/I^(-) redox pairs is prepared using simple calcination,solvothermal,and solution chemical deposition methods.The photocatalyst comprised mesoporous,thin g-C_(3)N_(4) nanosheets loaded on flower-like microspheres of BiOI with CdS quantum dots.The g-C_(3)N_(4)/BiOI/CdS double Z-scheme heterojunction has abundant active sites and in situ redox I_(3)^(-)/I^(-) mediators and shows quantum size effects,which are all conducive to enhancing the separation of photoinduced charges and increasing the photocatalytic degradation efficiency for bisphenol A,a model pollutant.Specifically,the heterojunction photocatalyst achieves a photocatalytic degradation efficiency for bisphenol A of 98.62%in 120 min and photocatalytic hydrogen production of 863.44 mmol h^(-1) g^(-1) on exposure to visible light.The excellent visible-light photocatalytic performance is as a result of the Z-scheme heterojunction,which extends absorption to the visible light region,as well as the I_(3)^(-)/I^(-) pairs,which accelerate photoinduced charge carrier transfer and separation,thus dramatically boosting the photocatalytic performance.In addition,the key role of the charge transfer across the indirect Z-scheme heterojunction has been elucidated and the transfer mechanism is confirmed based on the detection of intermediate I_(3)^(-)ions.Thus,this study provides guidelines for the design of indirect Z-scheme heterojunction photocatalysts.

Z-scheme N-doped K4Nb6O17/g-C3N4 heterojunction with superior visible-light-driven photocatalytic activity for organic pollutant removal and hydrogen production

A simple calcination method was employed to prepare a Z-scheme N-doped K4Nb6O17/g-C3N4(KCN)heterojunction photocatalyst,in which the electronic structure of K4Nb6O17 was regulated by N-doping,and g-C3N4 was formed both on the surface and within the interlayer spaces of K4Nb6O17.The KCN composite showed profoundly improved photocatalytic activity for both H2 generation and RhB degradation compared to its counterparts.This improved performance was attributed to the synergistic effects of N-doping,which broadened its light harvesting ability,and heterojunction formation,which increased the charge separation rate.The relatively low BET specific surface area of the KCN composite had little effect on its photocatalytic activity.Based on ESR spectroscopy studies,•O2^−,•OH,and h^+are the main active species in the photocatalytic degradation of RhB.Thus,it is reasonable to propose a Z-scheme photocatalytic mechanism over the KCN composite,which exhibits the dual advantages of efficient charge separation and high redox ability.Our work provides a simple approach for constructing large-scale Z-scheme heterojunction photocatalysts with high photocatalytic performance.

3D flower-like mesoporous Bi_(4)O_(5)I_(2)/MoS_(2)Z-scheme heterojunction with optimized photothermal-photocatalytic performance

3D flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2)/MoS_(2)Z-scheme layered heterojunction photocatalyst was fabricated by oil bath and hydrothermal methods.The heterojunction with narrow band gap of~1.95 eV extended the photoresponse to near-infrared region,which showed obvious photothermal effect due to the introduction of MoS_(2) with broad spectrum response.MoS_(2) nanosheets were anchored onto the surface of flower-like hierarchical mesoporous Bi_(4)O_(5)I_(2) nanosheets,thereby forming efficient layered heterojunctions,the solar-driven photocatalytic efficiency in degradation of highly toxic dichlorophenol and reduction of hexavalent chromium was improved to 98.5%and 99.2%,which was~4 and 7 times higher than that of the pristine Bi_(4)O_(5)I_(2),respectively.In addition,the photocatalytic hydrogen production rate reached 496.78 μmol h^(-1)g^(-1),which was~6 times higher than that of the pristine Bi_(4)O_(5)I_(2).The excellent photocatalytic performance can be ascribed to the promoted photothermal effect,as well as,the formation of compact Z-scheme layered heterojunctions.The 3D flower-like hierarchical mesoporous structure provided adequate surface active-sites,which was conducive to the mass transfer.Moreover,the high stability of the prepared photocatalyst further promoted its potential practical application.This strategy also provides new insights for fabricating layered Zscheme heterojunctions photocatalysts with highly photothermal-photocatalytic efficiency.

Fabrication of Z-scheme MoO3/Bi2O4 heterojunction photocatalyst with enhanced photocatalytic performance under visible light irradiation

Constructing Z-scheme heterojunction to improve the separation efficiency of photogenerated carriers of photocatalysts has gained extensive attention.In this work,we fabricated a novel Z-scheme MoO3/Bi2O4 heterojunction photocatalyst by a hydrothermal method.XPS analysis results indicated that strong interaction between MoO3 and Bi2O4 is generated,which contributes to charge transfer and separation of the photogenerated carriers.This was confirmed by photoluminescence(PL)and electrochemical impedance spectroscopy(EIS)tests.The photocatalytic performance of the as-synthesized photocatalysts was evaluated by degrading rhodamine B(RhB)in aqueous solution under visible light irradiation,showing that 15%MoO3/Bi2O4(15-MB)composite exhibited the highest photocatalytic activity,which is 2 times higher than that of Bi2O4.Besides,the heterojunction photocatalyst can keep good photocatalytic activity and stability after five recycles.Trapping experiments demonstrated that the dominant active radicals in photocatalytic reactions are superoxide radical( O2-)and holes(h+),indicating that the 15-MB composite is a Z-scheme photocatalyst.Finally,the mechanism of the Z-scheme MoO3/Bi2O4 composite for photo-degrading RhB in aqueous solution is proposed.This work provides a promising strategy for designing Bi-based Z-scheme heterojunction photocatalysts for highly efficient removal of environmental pollutants.

An effective CdS/Ti-Fe_(2)O_(3)heterojunction photoanode:Analyzing Z-scheme charge-transfer mechanism for enhanced photoelectrochemical water-oxidation activity

Z-scheme photocatalytic system has been regarded as a popular field of research in photoelectrochemical(PEC)water splitting.Among the many obstacles facing a Z-scheme photocatalytic system,the analysis methods of interfacial Z-scheme charge transfer still remain a significant challenge.Hence,in this study,CdS/Ti-Fe_(2)O_(3)heterojunction photoanodes are elaborately designed to explore the charge-transfer behavior in PEC water splitting.In this study,photophysical measurements,including the Kelvin probe measurement,surface photovoltage spectroscopy(SPV),and transient photovoltage spectroscopy(TPV),are used to monitor the migration behavior of photogenerated charges at the interface electric field of CdS/Ti-Fe_(2)O_(3)Z-scheme heterojunction photoanodes.The Kelvin probe and SPV measurements demonstrate that CdS/Ti-Fe_(2)O_(3)interfacial driving force favors the rapid transfer of photoexcited electrons to CdS.The double-beam strategy based on TPV indicates that more electrons of Ti-Fe_(2)O_(3)are combined with the holes of CdS owing to the intensive interface electric field.The results of these measurements successfully prove the Z-scheme migration mechanism of CdS/Ti-Fe_(2)O_(3)photoanodes.Benefiting from the desirable charge transfer at the interface electric field,CdS/Ti-Fe_(2)O_(3)photoanodes exhibit superior photocatalytic oxygen evolution reaction performance compared with that of pure Ti-Fe_(2)O_(3).The photocurrent density of the 25CdS/Ti-Fe_(2)O_(3)photoanode reaches 1.94 mA/cm^(2) at 1.23 V versus reversible hydrogen electrode without excess cocatalyst,and it is two times higher than that of pure Ti-Fe_(2)O_(3)photoanode.Therefore,an outstanding strategy is provided in this study to prove the Z-scheme charge-transfer mechanism of photocatalytic systems in PEC water splitting.

Experimental method to explore the adaptation degree of type-Ⅱand all-solid-state Z-scheme heterojunction structures in the same degradation system

TiO2 nanoparticles were prepared using the hydrothermal method and modified with CgN to syn-thesize a Type-Ⅱheterojunction semiconductor photocatalyst,TiO2-C;Na.In addition,a carbon layerwas coated onto the TiO2 nanoparticles and the obtained material was uniformly covered on thesurface of CaNa to form an all-solid-state Z-scheme semiconductor photocatalyst,TiO2-C-C3N4,Through characterization by XRD,XPS,SEM,TEM,BET,photoelectrochemical experiments,UV-visible diffuse reflection,and PL spectroscopy,the charge transfer mechanism and band gappositions for the composite photocatalysts were analyzed.The Type-Ⅱand all-solid-state Z-schemeheterojunction structures were compared.By combining microscopic internal mechanisms withmacroscopic experimental phenomena,the relationship between performance and structure wasverified.Experimental methods were used to explore the adaptation degree of different photocata-lytic mechanisms using the same degradation system.This study highlights effective photocatalystdesign to meet the requirements for specific degradation conditions.

Self-template-oriented synthesis of lead-free perovskite Cs_(3)Bi_(2)I_(9) nanosheets for boosting photocatalysis of CO_(2) reduction over Z-scheme heterojunction Cs_(3)Bi_(2)I_(9)/CeO_(2)

Lead halide perovskite (LHP) nanocrystals have been intensely studied as photocatalysts for artificial photosynthesis in recent years.However,the toxicity of lead in LHP seriously limits their potential for widespread applications.Herein,we first present the synthesis of 2D lead-free halide perovskite (Cs_(3)Bi_(2)I_(9)) nanosheets with self-template-oriented method,in which BiOI/Bi_(2)O_(2) nanosheets were used as the template and Bi ion source simultaneously.Through facile electrostatic self-assembly strategy,a Z-scheme heterojunction composed of Cs_(3)Bi_(2)I_(9)nanosheets and CeO_(2) nanosheets (Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1) was constructed as photocatalyst for the photo-reduction of CO_(2) coupled with the oxidation of H_(2)O.Due to the matching energy levels and the close interfacial contact between Cs_(3)Bi_(2)I_(9)and CeO_(2) nanosheets,the separation efficiency of the photogenerated carriers in Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1 composite was significantly improved.Consequently,the environment-friendly halide perovskite heterojunction Cs_(3)Bi_(2)I_(9)/CeO_(2)-3:1presents impressive photocatalytic activity for the reduction of CO_(2)to CH_(4)and CO with an electron consumption yield of 877.04μmol g^(-1),which is over 7 and 15 times higher than those of pristine Cs_(3)Bi_(2)I_(9)and CeO_(2)nanosheets,exceeding the yield of other reported bismuth-based perovskite for photocatalytic CO_(2)reduction.

Direct Z-scheme photochemical hybrid systems:Loading porphyrin-based metal-organic cages on graphitic-C_(3)N_(4) to dramatically enhance photocatalytic hydrogen evolution

The rational design of photochemical molecular device(PMD)and its hybrid system has great potential in improving the activity of photocatalytic hydrogen production.A series of Pd6L3 type metal-organic cages,denoted as MOC-Py-M(M=H,Cu,and Zn),are designed for PMDs by combining metalloporphyrin-based ligands with catalytically active Pd^(2+)centers.These metal-organic cages(MOCs)are first successfully hybridized with graphitic carbon nitride(g-C_(3)N_(4))to form direct Z-scheme heterogeneous MOC-Py-M/g-C_(3)N_(4)(M=H,Cu,and Zn)photocatalysts via π-πinteractions.Benefiting from its better light absorption ability,the MOC-Py-Zn/g-C_(3)N_(4) catalyst exhibits high H_(2) production activity under visible light(10348μmol g^(-1) h^(-1)),far superior to MOC-Py-H/g-C_(3)N_(4) and MOC-Py-Cu/g-C_(3)N_(4).Moreover,the MOC-Py-Zn/g-C_(3)N_(4) system obtains an enhanced turn over number(TON)value of 32616 within 100 h,outperforming the homogenous MOC-Py-Zn(TON of 507 within 100 h),which is one of the highest photochemical hybrid systems based on MOC for visible-light-driven hydrogen generation.This confirms the direct Z-scheme heterostructure can promote effective charge transfer,expand the visible light absorption region,and protect the cages from decomposition in MOC-Py-Zn/g-C_(3)N_(4).This work presents a creative example that direct Z-scheme PMD-based systems for effective and persistent hydrogen generation from water under visible light are obtained by heterogenization approach using homogeneous porphyrin-based MOCs and g-C_(3)N_(4) semiconductors.

Tuning electronic properties of the S2/graphene heterojunction by strains from density functional theory

Based on the density functional calculations, the structural and electronic properties of the WS2/graphene heterojunction under different strains are investigated. The calculated results show that unlike the free mono-layer WS2, the monolayer WS2 in the equilibrium WS2/graphene heterojunctionis characterized by indirect band gap due to the weak van der Waals interaction. The height of the schottky barrier for the WS2/graphene heterojunction is 0.13 eV, which is lower than the conventional metal/MoS2 contact. Moreover, the band properties and height of schottky barrier for WS2/graphene heterojunction can be tuned by strain. It is found that the height of the schottky barrier can be tuned to be near zero under an in-plane compressive strain, and the band gap of the WS2 in the heterojunction is turned into a direct band gap from the indirect band gap with the increasing schottky barrier height under an in-plane tensile strain. Our calculation results may provide a potential guidance for designing and fabricating the WS2-based field effect transistors.

Direct Z-scheme CdS-CdS Nanorod Arrays Photoanode: Synthesis,Characterization and Photoelectrochemical Performance

Direct Z-scheme CdO-CdS 1-dimensional nanorod arrays were constructed through a facile and simple hydrothermal process. The structure, morphology, photoelectrochemical properties and H2 evolution activity of this catalyst were investigated systematically. The morphology of the obtained nanorod is a regular hexagonal prism with 100-200 nm in diameter. The calcination temperature and time were optimized carefully to achieve the highest photoelectrochemical performance. The as-fabricated hybrid system achieved a photocurrent density up to 6.5 mA/cm2 and H2 evolution rate of 240 μmol·cm-2·h-1 at 0 V vs. Ag/AgCl, which is about 2-fold higher than that of the bare CdS nanorod arrays. The PEC performance exceeds those previously reported similar systems. A direct Z-scheme photocatalytic mechanism was proposed based on the structure and photoelectrochemical performance characterization results, which can well explain the high separation efficiency of photoinduced carriers and the excellent redox ability.

Boosted photocatalytic removal of NO using direct Z-scheme UiO-66-NH_(2)/Bi_(2)MoO_(6) nanoflowers heterojunction:mechanism insight and humidity effect

In practical applications,relative humidity in the air is a key factor affecting the photocatalytic removal of NO,which is often overlooked in previous studies.Here,we developed a direct Z-scheme UiO-66-NH_(2)/Bi_(2)MoO_(6)heterojunction with a nanoflower-like structure to systematically investigate the effect of relative humidity on photocatalytic removal of NO.The optimized heterojunction for the removal efficiency of NO was 71.6%at1.07 mg·m^(-3)NO concentration(relative humidity=10%),and the generation of NO_(2) was only 1.1%.Interestingly,with the increase in relative humidity,it showed a higher inhibition effect on NO_(2),while the removal of NO decreased slightly(8%),which might be attributed to the affinity effect of NO_(2) with water molecules and the competitive adsorption of H_(2)O and NO on the surface of the heterojunction photocatalysts.Furthermore,the reaction pathways of NO removal at the developed heterojunctions were revealed by in situ DRIFTS analysis.This work provides a novel vision for the development of direct Z-scheme heterojunction photocatalysts to effectively remove NO and inhibit the formation of toxic intermediate NO_(2) under different humidities.

Enhanced visible light photocatalytic H_2 production over Z-scheme g-C_3N_4 nansheets/WO_3 nanorods nanocomposites loaded with Ni(OH)_x cocatalysts

Novel WO3/g-C3N4/Ni（OH）x hybrids have been successfully synthesized by a two-step strategy of high temperature calcination and in situ photodeposition.Their photocatalytic performance was investigated using TEOA as a hole scavenger under visible light irradiation.The loading of WO3 and Ni（OH）x cocatalysts boosted the photocatalytic H2 evolution efficiency of g-C3N4.WO3/g-C3N4/Ni（OH）x with 20 wt%defective WO3 and 4.8 wt%Ni（OH）x showed the highest hydrogen production rate of 576 μmol/（g·h）,which was 5.7,10.8 and 230 times higher than those of g-C3N4/4.8 wt%Ni（OH）x,20 wt%WO3/C3N4 and g-C3N4 photocatalysts,respectively.The remarkably enhanced H2 evolution performance was ascribed to the combination effects of the Z-scheme heterojunction（WO3/g-C3N4） and loaded cocatalysts（Ni（OH）x）,which effectively inhibited the recombination of the photoexcited electron-hole pairs of g-C3N4 and improved both H2 evolution and TEOA oxidation kinetics.The electron spin resonance spectra of ·O2^- and ·OH radicals provided evidence for the Z-scheme charge separation mechanism.The loading of easily available Ni（OH）x cocatalysts on the Z-scheme WO3/g-C3N4 nanocomposites provided insights into constructing a robust multiple-heterojunction material for photocatalytic applications.

Construction of Ag_3PO_4/Ag_2MoO_4 Z-scheme heterogeneous photocatalyst for the remediation of organic pollutants

Hole/electron separation and charge transfer are the key processes for enhancing the visible-light photocatalysis performance of heterogeneous photocatalytic systems.To better utilize and understand these effects,binary Ag3PO4/Ag2MoO4 hybrid materials were fabricated by a facile solution-phase reaction and characterized systematically by X-ray diffraction（XRD）,energy-dispersive spectroscopy,Fourier transform infrared spectroscopy,Raman spectroscopy,field-emission scanning electron microscopy and ultraviolet-visible diffuse-reflectance spectroscopy.Under visible-light illumination,a heterogeneous Ag3PO4/Ag/Ag2MoO4 photocatalyst was constructed and demonstrated enhanced photocatalytic activity and photostability compared with pristine Ag3PO4toward the remediation of the organic dye rhodamine B.The Ag3PO4/Ag2MoO4 hybrid catalyst with8%mole fraction of Ag2MoO4 exhibited the highest photocatalytic activity toward the removal of typical dye molecules,including methyl orange,methylene blue and phenol aqueous solution.Moreover,the mechanism of the photocatalytic enhancement was investigated via hole- and radical-trapping experiments,photocurrent measurements,electrochemical impedance spectroscopy and XRD measurements.The XRD analysis revealed that metallic Ag nanoparticles formed initially on the surface of the Ag3PO4/Ag2MoO4 composites under visible-light illumination,leading to the generation of a Ag3PO4/Ag/Ag2MoO4 Z-scheme tandem photocatalytic system.The enhanced photocatalytic activity and stability were attributed to the formation of the Ag3PO4/Ag/Ag2MoO4Z-scheme heterojunction and surface plasmon resonance of photo-reduced Ag nanoparticles on the surface.Finally,a plasmonic Z-scheme photocatalytic mechanism was proposed.This work may provide new insights into the design and preparation of advanced visible-light photocatalytic materials and facilitate their practical application in environmental issues.