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.

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.

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.

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.

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.

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.

Electro-optical dual modulation on resistive switching behavior in BaTiO3/BiFeO3/TiO2 heterojunction

The novel BaTiO3/BiFeO3/TiO2 multilayer heterojunction is prepared on a fluorine-doped tinoxide(FTO) substrate by the sol–gel method. The results indicate that the Pt/Ba TiO3/BiFeO3/TiO2/FTO heterojunction exhibits stable bipolar resistive switching characteristic, good retention performance, and reversal characteristic. Under different pulse voltages and light fields, four stable resistance states can also be realized. The analysis shows that the main conduction mechanism of the resistive switching characteristic of the heterojunction is space charge limited current(SCLC) effect. After the comprehensive analysis of the band diagram and the P–E ferroelectric property of the multilayer heterojunction, we can deduce that the SCLC is formed by the effect of the oxygen vacancy which is controlled by ferroelectric polarizationmodulated change of interfacial barrier. And the effective photo-generated carrier also plays a regulatory role in resistance state(RS), which is formed by the double ferroelectric layer Ba TiO3/BiFeO3 under different light fields. This research is of potential application values for developing the multi-state non-volatile resistance random access memory(RRAM) devices based on ferroelectric materials.

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.

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.

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.

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.

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.

Novel Ag-bridged dual Z-scheme g-C_(3)N_(4)/BiOI/AgI plasmonic heterojunction: Exceptional photocatalytic activity towards tetracycline and the mechanism insight

Rational design and synthesis of highly efficient and robust photocatalysts with positive exciton splitting and interfacial charge transfer for environmental applications is critical.Herein,aiming at overcoming the common shortcomings of traditional photocatalysts such as weak photoresponsivity,rapid combination of photo-generated carriers and unstable structure,a novel Ag-bridged dual Z-scheme g-C_(3)N_(4)/BiOI/AgI plasmonic heterojunction was successfully synthesized using a facile method.Results showed that Ag-AgI nanoparticles and three-dimensional(3D)BiOI microspheres were decorated highly uniformly on the 3D porous g-C_(3)N_(4) nanosheet,resulting in a higher specific surface area and abundant active sites.The optimized 3D porous dual Z-scheme g-C_(3)N_(4)/BiOI/Ag-AgI manifested exceptional photocatalytic degradation efficiency of tetracycline(TC)in water with approximately 91.8%degradation efficiency within 165 min,outperforming majority of the reported g-C_(3)N_(4)-based photocatalysts.Moreover,g-C_(3)N_(4)/BiOI/Ag-AgI exhibited good stability in terms of activity and structure.In-depth radical scavenging and electron paramagnetic resonance(EPR)analyses confirmed the relative contributions of various scavengers.Mechanism analysis indicated that the improved photocatalytic performance and stability were ascribed to the highly ordered 3D porous framework,fast electron transfer of dual Z-scheme heterojunction,desirable photocatalytic performance of BiOI/AgI and synergistic effect of Ag plasmas.Therefore,the 3D porous Z-scheme g-C_(3)N_(4)/BiOI/Ag-AgI heterojunction had a good prospect for applications in water remediation.The current work provides new insight and useful guidance for designing novel structural photocatalysts for environment-related applications.

A direct Z-scheme 0Dα-Fe_(2)O_(3)/TiO_(2)heterojunction for enhanced photo-Fenton activity with low H_(2)O_(2)consumption

The insufficient F(Ⅲ)/Fe(Ⅱ)cycling rate resulted from high combination of photogenerated carriers severely hinders the photo-Fenton activity.In this work,0 dimensionalα-Fe_(2)O_(3)nanoclusters decorated Ti O_(2)heterojunction(FT-x)was prepared via in-situ phase transformation strategy.FT-200 exhibited the optimal photo-Fenton activity for 2,4-dichlorophenol degradation with the kinetic rate constant reaching1.0806 min^(-1)under low H_(2)O_(2)dosage(1 mmol/L),which was 126.1 and 202.8 times higher than that of Ti O_(2)andα-Fe_(2)O_(3).Radical quenching experiments and electron spin resonance spectra proved that·OH was the leading reactive specie.The enhanced photo-Fenton activity was attributed to the accelerated F(III)/Fe(II)cycling rate induced by the direct Z-Scheme charge transfer mechanism.Benefiting from the abundant·OH production,the dechlorinate ratios and mineralization ratios of multiple chlorophenol pollutants(2,4-dichlorophenol,4-chlorophenol,2,4,6-trichlorophenol)all exceeded 98%.The biotoxicity of chlorophenol wastewater was greatly reduced after the treatment by Light/H_(2)O_(2)/FT-200 system.Overall,this work constructed a low-cost and highly efficient photo-Fenton system for refractory organic wastewater treatment.

Built-in electric field intensified by photothermoelectric effect drives charge separation over Z-scheme 3D/2D In_(2)Se_(3)/PCN heterojunction for high-efficiency photocatalytic CO_(2) reduction

It is a challenging issue to further drive charge separation through the oriented design of Z-scheme het-erojunction in the exploitation of cost-effective photocatalytic materials.In this contribution,the unique Z-scheme 3D/2D In_(2)Se_(3)/PCN heterojunction is developed through implanting In_(2)Se_(3) microspheres on PCN nanosheets using an in situ growth technique,which acquires the effective CO generation activity from photocatalytic CO_(2) reduction(CO_(2)R).The CO yield of 4 h in the CO_(2)R reaction over the optimal In_(2)Se_(3)/PCN-15 sample reaches up to 11.40 and 2.41 times higher than that of individual PCN and In_(2)Se_(3),respectively.Such greatly enhanced photocatalytic performance is primarily the improvement of photo-generated carrier separation efficiency.To be more specific,the formed built-in electric field is signifi-cantly intensified by producing the temperature difference potential between In_(2)Se_(3) and PCN owing to the photothermoelectric effect of In_(2)Se_(3),which actuates the high-efficiency separation of photogenerated charge carriers along the Z-scheme transfer path in the In_(2)Se_(3)/PCN heterojunction.The effective strat-egy of enhancing the built-in electric field to drive photogenerated charge separation proposed in this work opens up an innovative avenue to design Z-scheme heterojunction applied to high-efficiency pho-tocatalytic reactions,such as hydrogen generation from water splitting,CO_(2)R,and degradation of organic pollutants.

Ti_(3)C_(2)-assisted construction of Z-scheme MIL-88A(Fe)/Ti_(3)C_(2)/RF heterojunction:Multifunctional photocatalysis-in-situ-self-Fenton catalyst

The applicability of the conventional Fenton reaction is limited due to several factors,including the high cost and slow redox cycle of Fe^(3+)/Fe^(2+),the requirement for harsh acidic conditions,and the insufficient presence of hydroxyl radicals for the ring-opening reaction.The combination of photocatalysis and Fenton technology to create a photocatalysis-in-situ-self-Fenton(PISF)system is a viable approach for addressing the inherent limitations of conventional Fenton reactions.Herein,a multifunctional PISF system,MIL-88A(Fe)/Ti_(3)C_(2) MXene/resorcinol-formaldehyde(MIL-88A(Fe)/Ti_(3)C_(2)/RF,MTR)Z-scheme heterojunction,was designed and constructed for degradating organics and inactivating bacteria.With the assistance of Ti_(3)C_(2),the degradation rate of TC by MTR catalyst was 4.8 times that of MIL-88A(Fe)/RF catalyst under visible light irradiation.Meanwhile,good degradation performance was maintained after 5 cycling tests.The remarkable TC removal efficiency(97.4%)and durability were attributed to the synergistic effect of the photocatalytic reaction and Fenton reaction.The photoinduced holes(h^(+))assist hydroxyl radicals(·OH)generated by the Fenton reaction for deeply mineralizing TC.The degradation intermediates,potential degradation pathways,and intermediates toxicity were comprehensively investigated to gain a deeper understanding of the catalytic process.Moreover,under visible light irradiation,the MTR killed 97.8%of E.coli and 94.9%of S.aureus within 120 min,demonstrating good antibacterial activity.This work provides a novel strategy to design PISF catalysts for environmental remediation.

Coupled Cu doping and Z-scheme heterojunction for synergistically enhanced tetracycline photodegradation

Semiconductor-based photocatalysis by utilizing solar energy for sustainable organic pollutant elimination has been a promising tactic to alleviate environmental issues.Nevertheless,the development of robust and efficient photocatalysts to degrade organic pollutants still faces major challenges because of insufficient charge separation.Here we design and fabricate a heterojunction consisting of copper,carbon-modified TiO_(2),and sulfur-doped g-C_(3)N_(4)nanosheets(i.e.,S-C_(3)N_(4)/Cu/C-TiO_(2)).The heterostructure affords a remarkable synergistic photocatalysis for tetracycline hydrochloride degradation,achieving an 82.6%removal efficiency within 30 min under visible light irradiation,about 15.4 and 7.3 times higher than that of S-C_(3)N_(4)and C-TiO_(2),respectively.The superior performance is attributed to the synergy between Cu doping and the Z-scheme heterojunction,which not only enhances the interfacial electric field effect,facilitating charge separation,but also boosts the redox capability.The charge carrier transfer between Cu/C-TiO_(2)and S-C_(3)N_(4)follows a Z-scheme,as verified by trapping experiments,electron spin-resonance spectroscopy,and density functional theory calculations.Furthermore,the tetracycline hydrochloride degradation pathways are enunciated by liquid chromatograph mass spectrometry analysis.This work provides an effective approach for constructing high-performance photocatalysts that have potential in environmental remediation.

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.