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.

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.

Achieving highly-efficient H2S gas sensor by flower-like SnO_(2)–SnO/porous GaN heterojunction

A flower-like SnO_(2)–SnO/porous Ga N(FSS/PGaN) heterojunction was fabricated for the first time via a facile spraying process, and the whole process also involved hydrothermal preparation of FSS and electrochemical wet etching of GaN,and SnO_(2)–SnO composites with p–n junctions were loaded onto PGaN surface directly applied to H_(2)S sensor. Meanwhile,the excellent transport capability of heterojunction between FSS and PGaN facilitates electron transfer, that is, a response time as short as 65 s and a release time up to 27 s can be achieved merely at 150℃ under 50 ppm H_(2)S concentration, which has laid a reasonable theoretical and experimental foundation for the subsequent PGaN-based heterojunction gas sensor.The lowering working temperature and high sensitivity(23.5 at 200 ppm H2S) are attributed to the structure of PGaN itself and the heterojunction between SnO_(2)–SnO and PGaN. In addition, the as-obtained sensor showed ultra-high test stability.The simple design strategy of FSS/PGaN-based H_(2)S sensor highlights its potential in various applications.

N-doped graphene quantum dot-decorated N-TiO2/P-doped porous hollow g-C_(3)N_(4) nanotube composite photocatalysts for antibiotic photodegradation and H2 production

Exclusive responsiveness to ultraviolet light (~3.2 eV) and high photogenerated charge recombination rate are the two primary drawbacks of pure TiO_(2). We combined N-doped graphene quantum dots (N-GQDs), morphology regulation, and heterojunction construction strategies to synthesize N-GQD/N-doped TiO_(2)/P-doped porous hollow g-C_(3)N_(4) nanotube (PCN) composite photocatalysts (denoted as G-TPCN). The optimal sample (G-TPCN doped with 0.1wt% N-GQD, denoted as 0.1% G-TPCN) exhibits significantly enhanced photoabsorption, which is attributed to the change in bandgap caused by elemental doping (P and N), the improved light-harvesting resulting from the tube structure, and the upconversion effect of N-GQDs. In addition, the internal charge separation and transfer capability of0.1% G-TPCN are dramatically boosted, and its carrier concentration is 3.7, 2.3, and 1.9 times that of N-TiO_(2), PCN, and N-TiO_(2)/PCN(TPCN-1), respectively. This phenomenon is attributed to the formation of Z-scheme heterojunction between N-TiO_(2) and PCNs, the excellent electron conduction ability of N-GQDs, and the short transfer distance caused by the porous nanotube structure. Compared with those of N-TiO_(2), PCNs, and TPCN-1, the H2 production activity of 0.1%G-TPCN under visible light is enhanced by 12.4, 2.3, and 1.4times, respectively, and its ciprofloxacin (CIP) degradation rate is increased by 7.9, 5.7, and 2.9 times, respectively. The optimized performance benefits from excellent photoresponsiveness and improved carrier separation and migration efficiencies. Finally, the photocatalytic mechanism of 0.1% G-TPCN and five possible degradation pathways of CIP are proposed. This study clarifies the mechanism of multiple modification strategies to synergistically improve the photocatalytic performance of 0.1% G-TPCN and provides a potential strategy for rationally designing novel photocatalysts for environmental remediation and solar energy conversion.

RECTIFYING EFFECT OF POLYANILINE(PANI)/N-TYPE POROUS SILICONE HETEROJUNCTION

Heterojunctions between polyaniline (PANI) and n-type porous silicon (PS), Al/PS-PANI/Au cell, were fabricated, and the rectifying parameters of this heterojunction diode were measured as a function of the preparation conditions of PANI and PS, the electronic structure of PANI as well as cell structure. The rectifying parameters of Al/PS-PANI/Au cell were determined to be gamma = 1.8x10(1) similar to 1.0x10(5) for the rectifying ratio at 3V, n = 3 similar to 12 for the ideal factor, j(0) = 8.0x10(-5) similar to 5.6x10(-2) mA/cm(2) for the reversed saturated current density, and phi(0) = 0.67 similar to 0.83 V for the barrier height, respectively. The best rectifying heterojunction diode made between PANI and n-type PS with higher rectifying factor (gamma = 1.0x10(5) at 3V), output current (>1500 mA/cm(2) at 3V) and lower ideal factor (n = 3.3) was obtained by preventing the oxidation of PS before evaporating Al electrode.

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.

HETEROJUNCTION DIODES OF POROUS SILICON WITH SOLUBLE POLYANILINE

Two kinds of heterojunction diodes of porous silicon (PS) with soluble polyaniline (PANI) were fabricated. One is a heterojunction diode of PS with water-soluble copolymer of polyaniline (PAOABSA), Al/PS-PAOABSA/Au cell as rectifying diode. Another is a heterojunction diode of PS with soluble polyaniline doped with DBSA, Al/PS-PANI (DBSA)/Au cell as light emitting diode (LED). The rectifying characteristics of the rectifying diodes were measured as a function of the degree of sulfonation and thickness of the copolymers, as well as oxidation of PS. The rectifying ratio of the heterojunction can reach 5.0x10(4) at +/-3 V bias. For the LED, the photoluminescence (PL) and electroluminescence (EL) spectra were measured and discussed.

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.

Reactive template-derived interfacial engineering of CoP/CoO heterostructured porous nanotubes towards superior electrocatalytic hydrogen evolution

The development of economical,efficient,and robust electrocatalysts toward the hydrogen evolution reaction(HER)is highly imperative for the rapid advancement of renewable H2 energy-associated technologies.Extensive utilization of the heterointerface effect can endow the catalysts with remarkably boosted electrocatalytic performance due to the modified electronic state of active sites.Herein,we demonstrate deliberate crafting of CoP/CoO heterojunction porous nanotubes(abbreviated as CoP/CoO PNTs hereafter)using a self-sacrificial template-engaged strategy.Precise control over the Kirkendall diffusion process of the presynthesized cobalt–aspartic acid complex nanowires is indispensable for the formation of CoP/CoO heterostructures.The topochemical transformation strategy of the reactive templates enables uniform and maximized construction of CoP/CoO heterojunctions throughout all the porous nanotubes.The establishment of CoP/CoO heterojunctions could considerably modify the electronic configuration of the active sites and also improve the electric conductivity,which endows the resultant CoP/CoO PNTs with enhanced intrinsic activity.Simultaneously,the hollow and porous nanotube architectures allow sufficient accessibility of exterior/interior surfaces and molecular permeability,drastically promoting the reaction kinetics.Consequently,when used as HER electrocatalysts,the well-designed CoP/CoO PNTs show Pt-like activity,with an overpotential of only 61 mV at 10mA cm^(−2) and excellent stability in 1.0M KOH medium,exceeding those of the vast majority of the previously reported nonprecious candidates.Density functional theory calculations further substantiate that the construction of CoP/CoO heterojunctions enables optimization of the Gibbs free energies for water adsorption and H adsorption,resulting in boosted HER intrinsic activity.The present study may provide in-depth insights into the fundamental mechanisms of heterojunction-induced electronic regulation,which may pave the way for the rational design of advanced Earth-abundant electrocatalysts in the future.

Rationally construction of atomic-precise interfacial charge transfer channel and strong build-in electric field in nanocluster-based Zscheme heterojunctions with enhanced photocatalytic hydrogen production

The lack of effective charge transfer driving force and channel limits the electron directional migration in nanoclusters(NC)-based heterostructures,resulting in poor photocatalytic performance.Herein,a Z-scheme NC-based heterojunction(Pt1Ag28-BTT/CoP,BTT=1,3,5-benzenetrithiol)with strong internal electric field is constructed via interfacial Co-S bond,which exhibits an absolutely superiority in photocatalytic performance with 24.89 mmol·h^(−1)·g−1 H_(2)production rate,25.77%apparent quantum yield at 420 nm,and~100%activity retention in stability,compared with Pt1Ag28-BDT/CoP(BDT=1,3-benzenedithiol),Ag29-BDT/CoP,and CoP.The enhanced catalytic performance is contributed by the dual modulation strategy of inner core and outer shell of NC,wherein,the center Pt single atom doping regulates the band structure of NC to match well with CoP,builds internal electric field,and then drives photogenerated electrons steering;the accurate surface S modification promotes the formation of Co-S atomic-precise interface channel for further high-efficient Z-scheme charge directional migration.This work opens a new avenue for designing NC-based heterojunction with matchable band structure and valid interfacial charge transfer.

NiCo_(2)O_(4)/BiOCl/Bi_(24)O_(31)Br_(10) ternary Z-scheme heterojunction enhance peroxymonosulfate activation under visible light: Catalyst synthesis and reaction mechanism

The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position,promoting the synergistic coupling of photocatalysis and peroxymonosulfate(PMS) activation.In order to fully utilize the luminous energy and realize the efficient activation of PMS,this work achieved successful construction of NiCo_(2)O_(4)/BiOCl/Bi_(24)O_(31)Br_(10) ternary Z-scheme heterojunction by simultaneously synthesizing BiOCl and NiCo_(2)O_(4) with NiCl_(2) and CoCl_(2) as the precursors.The intercalated BiOCl could serve as a carrier migration ladder to further achieve the spatial separation of electron-hole pairs,so that the oxidation and reduction processes separately occurred in different regions.Compared with the reported catalysts,the as-prepared composites exhibited the enhanced removal efficiency for tetracycline hydrochloride(TCH) in the visible light/PMS system,with a degradation efficiency of 85.30%in 2 min,and possessed good stability.Z-scheme heterojunction was shown to be beneficial for maximizing the superiority of photo-assisted Fenton-like reaction system.The experimental and characterization results confirmed that both non-radicals(^(1)O_(2)) and radicals(SO_(5)^(·-) and SO_(4)^(·-)) were involved in the reaction process and the SO_(5)^(·-)generated by the oxidation of PMS played a crucial role in the TCH degradation.The possible reaction mechanism was finally proposed.This study provided new insight into the Z-scheme heterostructure to promote the photo-assisted Fenton-like reaction.

2D/2D covalent organic framework/CdS Z-scheme heterojunction for enhanced photocatalytic H_(2) evolution:Insights into interfacial charge transfer mechanism

Covalent organic frameworks(COFs)with high crystallinity and flexible designability have been consid-ered as promising candidates for photocatalytic hydrogen evolution.However,the existence of unpropi-tious exciton effects in COFs leads to poor charge separation,and thus results in low photocatalytic effi-ciency.Herein,to improve the photoelectron migration efficiency,we designed a 2D/2D organic/inorganic direct Z-scheme COF-based heterojunction(TpTAP/CdS),by the in-situ growing of CdS nanosheets on the COF copolymerized via 2,4,6-tris(4-aminophenyl)-1,3,5-triazine(TAP)and 1,3,5-triformylphloroglucinol(Tp).The femtosecond transient absorption(fs-TA)decay kinetics of TpTAP-COF and TpTAP/CdS further reveal the processes of shallow electron trapping and the recombination of the free photogenerated electron-hole pairs.In particular,the transient absorption traces for TpTAP-COF and TpTAP/CdS normal-ized to the photoinduced absorption peak can effectively verify the Z-scheme charge transfer between TpTAP-COF and CdS,which could enhance the charge mobility and separation,thus reducing the pho-tocorrosion of CdS.Additionally,ultraviolet photoelectron spectroscopy(UPS),in-situ X-ray photoelec-tron spectroscopy(XPS),transient photovoltage measurements,and electron spin resonance(ESR)spec-troscopy further confirm the establishment of the internal electric field(IEF).This work demonstrates the important role of COFs in the construction of 2D/2D organic/inorganic direct Z-scheme heterojunctions and offers a new avenue to explain the criticality of dynamics of the photogenerated carriers for the construction of Z-scheme heterojunctions.

ZnFe_(2)O_(4)/BiVO_(4)Z-scheme heterojunction for efficient visible-light photocatalytic degradation of ciprofloxacin

A novel Z-scheme ZnFe_(2)O_(4)/BiVO_(4)heterojunction photocatalyst was successfully synthesized using a convenient solvothermal method and applied in the visible light photocatalytic degradation of ciprofloxacin,which is a typical antibiotic contaminant in wastewater.The heterostructure of as-synthesized catalysts was confirmed using X-ray diffraction,scanning electron microscopy,transmission electron microscopy and X-ray photoelectron spectroscopy characterizations.Compared with the singlephase counterparts,ZnFe_(2)O_(4)/BiVO_(4)demonstrated considerably enhanced photogenerated charge separation efficiencies because of the Z-scheme transfer mechanism of electrons between the composite photocatalysts.Consequently,the 30%ZnFe_(2)O_(4)/BiVO_(4)catalyst afforded a degradation rate of up to 97%of 20 mg/L ciprofloxacin under 30 min of visible light irradiation with a total organic carbon removal rate of 50%,which is an excellent activity compared with ever reported BiVO_(4)-based catalysts.In addition,the liquid chromatography-mass spectrometry and quantitative structure-activity relationships model analyses demonstrated that the toxicity of the intermediates was lower than that of the parent ciprofloxacin.Moreover,the as-synthesized ZnFe_(2)O_(4)/BiVO_(4)heterojunctions were quite stable and could be reused at least four times.This study thus provides a promising Z-scheme heterojunction photocatalyst for the efficient removal and detoxication of antibiotic pollutants from wastewater.

Face-to-face heterojunctions within 2D/2D porous NiCo oxyphosphide/g-C_(3)N_(4)towards efficient and stable photocatalytic H_(2)evolution

Constructing 2D/2D face-to-face heterojunctions is believed to be an effective strategy to enhance photocatalytic performance due to the enlarged contact interface and increased surface active sites.Herein,2D porous NiCo oxyphosphide(NiCoOP)was synthesized for the first time and coupled with graphitic carbon nitride(g-C_(3)N_(4))nanosheets to form 2D/2D heterojunctions via an in-situ phosphating method.The optimal 4 wt.%2D/2D NiCoOP/g-C_(3)N_(4)(OPCN)photocatalyst achieves a hydrogen evolution rate of 1.4 mmol·h^(−1)·g^(−1),which is 33 times higher than that of pure g-C_(3)N_(4).The greatly improved photocatalytic performance of the composite photocatalysts could be attributed to the formation of interfacial surface bonding states and sufficient charge transfer channels for accelerating carrier separation and transfer and the porous structure of NiCoOP nanosheets with abundant surface active sites for promoting surface reactions.Amazingly,the 2D/2D OPCN composite photocatalysts also exhibit superior stability during photocatalytic reactions.This study not only designs new noble-metal-free NiCoOP/g-C_(3)N_(4)composite photocatalysts but also provides a new sight in fabricating face-to-face 2D/2D heterojunctions for their application in energy conversion areas.

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.

Two-dimensional porous Cu-CuO nanosheets: Integration of heterojunction and morphology engineering to achieve high-effective and stable reduction of the aromatic nitro-compounds

The morphology and heterojunction engineering are effective ways to boost the performance of Cubased catalysts. Herein, we have reported the designed synthesis of two-dimensional Cu-Cu O heterojunction nanosheets(2D Cu-Cu O NS) based on 3-aminopropyl-triethoxysilane(APTES, KH550) aided synthetic strategy. The APTES can act as both the ligand and alkali(-OH) source to guide the large-scale synthesis of 2D Cu-based precursor, which can transform into 2D Cu-Cu O NS by the controllable post-treatment.The Si species from APTES can protect the particles from the severe aggregation and growth, guaranteeing the formation of 2D sheets composed of small-sized Cu-Cu O heterojunction(about 20 nm). The heterojunction interfaces can provide plentiful active sites to boost the catalytic ability. The 2D sheets can provide large accessible surface, being conducive to the contact of the catalyst and reactants. Benefiting from above virtues, the 2D Cu-Cu O NS showed the superior catalytic performance for the reduction of a series of nitro compounds, being superior to most reported non-noble metal-based catalysts. Notably,it exhibited good re-cycled performance with no obvious performance degradation after 10 consecutive catalysis. The present study will be promising to promote the application of the Cu-based catalysts, due to its ability to control the morphology and potential for the large-scale synthesis.

Construction of 3D/2D indium vanadate /graphite carbon nitride with nitrogen defects Z-scheme heterojunction for improving photocatalytic carbon dioxide reduction

Indium vanadate (InVO4 ) possesses excellent potential in photocatalytic carbon dioxide (CO_(2) ) reduction, but further modifications of reducing charge recombination and increasing active sites are still needed. Herein, InVO4 /g-C3 N4 (InVO-CN) heterojunction composite photocatalysts were prepared via in situ formation of InVO4 nanoparticles on the lamellar structure of graphite carbon nitride (g-C3 N4 ) containing nitrogen (N) defects. Among these composites, 30% InVO-CN showed the best photoreduction performance for CO_(2) at normal temperature and pressure without sacrificial agent (carbon monoxide, CO: 20.14 μmol g–1 h–1;methane, CH4 : 3.46 μmol g–1 h–1 ), which were 1.8 and 2.8 times higher than these of pure g-C3 N4 and InVO4 . The excellent performance could be attributed to the enhancement of CO_(2) adsorption, and most importantly, the enhanced charge carrier separation and reduction capacity induced by the formation of Z-scheme heterojunction between InVO4 and g-C3 N4 . In this work, intimate heterojunction interfaces between materials were formed by introducing g-C3 N4 with defects in InVO4 , which provides a promising modification scheme.

Construction of 2D/2D Z-scheme MnO_(2-x)/g-C_(3)N_(4) photocatalyst for efficient nitrogen fixation to ammonia

Reducing nitrogen to ammonia with solar energy has become a wide concern when it comes to photocatalysis research.It is considered to be one of the more promising alternate options for the conventional Haber-Bosch cycle.Herein,2D g-C_(3)N_(4)composites with modifying ultrathin sheet MnO_(2-x)were prepared and used as nitrogen fixation photocatalyst.With the assistance of the nature of MnO_(2-x),the generation rate of NH_(3)reached 225 mmol g^(-1)h^(-1),which is more than twice over the rate of pristine 2D g-C_(3)N_(4)(107 mmol g^(-1)h^(-1)).The presence of ultrathin sheet MnO_(2-x)shortens the gap of the carriers to the surface of photocatalyst.Thus the speed of electron transfer gets increased.Besides,the construction of Z-scheme heterojunction boosts the separation and migration of photogenerated carriers.As a result,the nitrogen reduction reaction(NRR)performance gets enhanced.The work may provide an example of promoting the NRR performance of non-metallic compound.