In the midst of the rapid advancement of photocatalysis,direct Z-scheme heterojunction photocatalysts have emerged as a powerful solution to address environmental challenges and the looming energy crisis.The precise e...In the midst of the rapid advancement of photocatalysis,direct Z-scheme heterojunction photocatalysts have emerged as a powerful solution to address environmental challenges and the looming energy crisis.The precise engineering of direct Z-scheme heterojunction photocatalysts proves highly beneficial in optimizing their elec-tronic structure,ultimately enhancing their photocatalytic performance.Notably,graphitic carbon nitride(g-C_(3)N_(4))has recently gained recognition as a leading candidate for the creation of direct Z-scheme heterojunctions,owing to its favorable attributes such as a moderate band-gap(2.7 eV),high reduction potential and abundant active sites.In this review,we offer a concise overview of the fundamental principles and recent advancements in g-C_(3)N_(4)-based direct Z-scheme photocatalytic systems.Furthermore,we delve into the various practical applica-tions of g-C_(3)N_(4)-based direct Z-scheme photocatalysts,specifically in the realms of energy conversion and envi-ronmental remediation.These applications include the removal of contaminant pollutants through photocatalytic degradation,water splitting(comprising H_(2)-generation,O_(2)-evolution,and overall water splitting),and CO_(2)reduction.Additionally,we present comprehensive characterization methods and strategies aimed at further enhancing the photocatalytic activity of g-C_(3)N_(4)-based direct Z-scheme photocatalytic systems.To conclude,this review offers summarizing insights and a brief discussion on future challenges and prospects pertaining to g-C_(3)N_(4)-based direct Z-scheme photocatalysts.We believe that this review will inspire continued exploration and foster a deeper understanding of the groundbreaking possibilities within photocatalytic activity.This also provides valuable guidance for the design and construction of innovative direct Z-scheme photocatalysts.展开更多
Photocatalytic water splitting by semiconductors is a promising technology to produce clean H_(2) fuel,but the efficiency is restrained seriously by the high overpotential of the H_(2)-evolution reaction together with...Photocatalytic water splitting by semiconductors is a promising technology to produce clean H_(2) fuel,but the efficiency is restrained seriously by the high overpotential of the H_(2)-evolution reaction together with the high recombination rate of photoinduced charges.To enhance H_(2) production,it is highly desirable yet challenging to explore an efficient reductive cocatalyst and place it precisely on the right sites of the photocatalyst surface to work the proton reduction reaction exclusively.Herein,the metalloid NixP cocatalyst is exactly positioned on the Z-scheme Cd_(0.5)Zn_(0.5)S/NiTiO_(3)(CZS/NTO)heterostructure through a facile photodeposition strategy,which renders the cocatalyst form solely at the electron-collecting locations.It is revealed that the directional transfer of photoexcited electrons from Cd_(0.5)Zn_(0.5)S to Ni_(x)P suppresses the quenching of charge carriers.Under visible light,the CZS/NTO hybrid loaded with the Ni_(x)P cocatalyst exhibits an optimal H_(2) yield rate of 1103μmol h^(-1)(i.e.,27.57 mmol h^(-1)g^(-1)),which is about twofold of pristine CZS/NTO and comparable to the counterpart deposited with the Pt cocatalyst.Besides,the high apparent quantum yield(AQY)of 56%is reached at 400 nm.Further,the mechanisms of the cocatalyst formation and the H2 generation reaction are discussed in detail.展开更多
Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion ...Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.展开更多
Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spect...Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.展开更多
This study focused on the development and characterization of TiO<sub>2</sub>-PES composite fibers with varying TiO<sub>2</sub> loading amounts using a phase inversion process. The resulting co...This study focused on the development and characterization of TiO<sub>2</sub>-PES composite fibers with varying TiO<sub>2</sub> loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO<sub>2</sub> nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO<sub>2</sub> composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO<sub>2</sub> composite fibers as promising photocatalysts for ammonia removal in water treatment applications.展开更多
It is highly desirable to simulate natural photosynthesis by using sunlight to drive the overall water splitting without using external bias and sacrificial agent.Herein,few-layer monoclinic BiVO4 nanosheets(BVNS)with...It is highly desirable to simulate natural photosynthesis by using sunlight to drive the overall water splitting without using external bias and sacrificial agent.Herein,few-layer monoclinic BiVO4 nanosheets(BVNS)with a thickness of(∼)4.3 nm,exposed(010)facets and abundant oxygen vacancies are fabricated using graphene oxide dots as templating reagent.After decorating with asymmetric chromium porphyrin derivative bearing one benzoic acid and three phenyls as meso-position substituents(chromium-5-(4-carboxyphenyl)-10,15,20-triphenylporphrin,CrmTPP)and PtOx cocatalyst,the obtained two-dimensional(2D)hybrid nanocomposite(BVNS/CrmTPP/Pt)with an optimal component ratio delivers a robust overall water splitting performance with a relatively high apparent quantum yield(8.67%)at 400 nm monochromatic light.The ultrathin structure and widely distributed oxygen vacancies on the exposed(010)facets of BVNS not only endow strong and intimate contact with the decorated CrmTPP molecules to promote a two-step excitation Z-scheme charge transfer mechanism for preserving the high redox ability of the photogenerated charge carriers,but also alleviate their recombination,and thus causing the robust overall water splitting performance of the 2D hybrid nanocomposites.The present results provide a novel strategy to construct highly efficient artificial photosynthetic system for overall water splitting.展开更多
The major findings in this report are(ⅰ)development of nanocomposite photocatalyst working through Z-scheme charge transfer pathway across the heterojunction,(ⅱ)utilization of direct sunlight as the photo-source,and...The major findings in this report are(ⅰ)development of nanocomposite photocatalyst working through Z-scheme charge transfer pathway across the heterojunction,(ⅱ)utilization of direct sunlight as the photo-source,and(ⅲ)prospect of ligand-hole in photocatalysis through enhanced sub-band gap absorption,The photocatalysts,namely LaNiO_(3),g-C_(3)N_(4) and LaNiO_(3)/g-C_(3)N_(4) nanocomposites were synthesized via facile route and were characterized for their structure,morphology,microstructure,texture,elemental mapping and surface oxidation states by using several physicochemical techniques.The photocatalytic performance of the nanocomposite was tested through the degradation of hazardous azo dye pollutants,namely reactive black 5 and methylene blue as well as the colorless antibiotic-pollutant tetracycline hydrochloride in aqueous solution in presence of natural sunlight with excellent recycling activity.The 10%LaNiO_(3)/g-C_(3)N_(4) nanocomposite sample shows the best catalytic activity,degrading respectively 94%,98.6%and 88.1%of reactive black 5,methylene blue and tetracycline hydrochloride in60,180 and 120 min.The photocatalytic activity of the nanocomposite phase is several times superior to that of the pure phases.The improvements of photocatalytic activity of g-C_(3)N_(4) in the nanocomposite have been rationalized through the construction of direct Z-scheme heterojunction and suppression of electron-hole pair recombination efficiency.The enhanced photo-absorption of the nanocomposite can possibly be related to sub-bandgap absorption,which is associated to the midgap state originating from ligand-hole formation or defects in the structure.The photodegradation process is mediated through the formation of super oxide radical(O_(2))and hole(h^(+))as the main responsible species.展开更多
With continuous consumption of nonrenewable energy,solar energy has been predicted to play an essential role in meeting the energy demands and miti gating environmental issues in the future.Despite being green,clean a...With continuous consumption of nonrenewable energy,solar energy has been predicted to play an essential role in meeting the energy demands and miti gating environmental issues in the future.Despite being green,clean and pollution-free energy,solar energy cannot be adopted directly as it cannot provide sufficiently high energy density to work in the absence of machinery.Thus,it is necessary to develop an effective strategy to convert and store solar energy into chemical energy to achieve social sustainable development using solar energy as the main power source.Photocatalysis,in which semi conductor photocatalysts play a key role,is one of the most promising can didates for realising the effective utilisation of sunlight in a green,low-cost and environmentally friendly method.The photocatalytic efficiency of photo catalysts is considerably influenced by their compositions.Among the various heterostructures,Z-scheme heterojunction is one of the most interesting ar chitecture due to its outstanding performance and excellent artificial imitation of photosynthesis.Z-scheme photocatalysts have attracted considerable at tention in the past few decades.Herein,we review contemporary Z-scheme systems,with a particular focus on mechanistic breakthroughs,and highlight current state-of-the-art systems.Z-type photocatalysts are classified as tradi tional,all-solid-state,direct Z-schemes and S-scheme photocatalysts.The morphology,characterisation and working mechanism of each type of Z-scheme are discussed in detail.Furthermore,the applications of Z-scheme in photoelectrochemical water splitting,nitrogen fixation,pollutant degrada tion and carbon dioxide reduction are illustrated.Finally,we outline the main challenges and potential advances in Z-scheme architectures,as well as their future development directions.展开更多
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 cyc...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.展开更多
Improving the separation efficiency of photogenerated carriers and broadening the light absorption range of the photocatalyst are two important factors for improving the performance of the photocatalyst.In this paper,...Improving the separation efficiency of photogenerated carriers and broadening the light absorption range of the photocatalyst are two important factors for improving the performance of the photocatalyst.In this paper,a new and efficient Z-scheme Cd S/iron phthalocyanine(Cd S/Fe Pc)core-shell nanostructure composite material is prepared by a simple solid-phase reaction method.There are two key points in the preparation of composite materials:one is that hydrogen bonding energy is closely connected with Fe Pc,another is that Fe Pc can be uniformly assembled on Cd S nanoparticles.The photocatalytic hydrogen evolution(PHE)of the Cd S/Fe Pc nanocomposite(73.01μmol/h)is 2.6 times higher than that of pure Cd S(26.67μmol/h).In addition,after 4 photocatalytic cycles,the PHE of the Cd S/Fe Pc composite is still 92.3%of the first cycle.There are three reasons for this situation:(1)The Z-scheme heterojunction is formed to improve the separation efficiency of photogenerated carriers;(2)Fe Pc expands the visible light absorption range of Cd S;(3)The large core-shell contact area is favorable for the separation of photo-induced carriers at the interfaces.This research is conducive to the further development of new photocatalytic materials with high efficiency,low cost and simple preparation.展开更多
In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles(NPs) were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the...In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles(NPs) were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the geothermal water served as the chlorine source. Then the photocatalytic activity was investigated by degradation of 4-Aminobenzoic acid(4-ABA) under visible-light irradiation. It was found that the as-prepared 50 wt% Ag/Ag Cl/WO3 photocatalyst showed the highest photocatalytic efficiency with 25.12 and 3.53 times higher than those of pure WO3 and Ag/Ag Cl, respectively. The active species trapping experiments indicated that h+and ·O2-were key factors in 4-ABA photodegradation process. The possible plasmonic Z-scheme photocatalytic mechanism of photocatalytic reaction for 4-ABA degradation was proposed based on systematical characterizations. We hope this paper could give new ideas for further exploiting geothermal energy to design and fabricate highly efficient visible-light-driven photocatalysts for environmental remediation.展开更多
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 exten...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.展开更多
Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalyt...Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalytic performance.Among them,Bi-based photocatalysts have become one of the most popular research topics due to their suitable band gaps,unique layered structures,and physicochemical properties.In this review,Bi-based photocatalysts(BiOX,BiVO_(4),Bi_(2)S_(3),Bi_(2)MoO_(6),and other Bi-based photocatalysts)have been summarized in the field of photocatalysis,including their applications of the removal of organic pollutants,hydrogen production,oxygen production etc.The preparation strategies on how to improve the photocatalytic performance and the possible photocatalytic mechanism are also summarized,which could supply new insights for fabricating high-efficient Bi-based photocatalysts.Finally,we summarize the current challenges and make a reasonable outlook on the future development direction of Bi-based photocatalysts.展开更多
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...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.展开更多
Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesize...Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride(PMDA) and various diamine monomers(melamine(MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 ℃/min(MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.展开更多
Treating waste with a waste material using freely available solar energy is the most effective way towards sustainable future.In this study,a novel photocatalyst,partly derived from waste material from the coal indust...Treating waste with a waste material using freely available solar energy is the most effective way towards sustainable future.In this study,a novel photocatalyst,partly derived from waste material from the coal industry,was developed.Fly ash hybridized with ZnO(FAeZn)was synthesized as a potential photocatalyst for dye discoloration.The synthesized photocatalyst was characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,and ultravioletevisible/near infra-red spectroscopy.The photocatalytic activity was examined with the discoloration of methylene blue used as synthetic dye wastewater.All the experiments were performed in direct sunlight.The photocatalytic performance of FAeZn was found to be better than that of ZnO and the conventionally popular TiO2.The LangmuireHinshelwood model rate constant values of ZnO,TiO2,and FAeZn were found to be 0.016 min1,0.017 min1,and 0.020 min1,respectively.There were two reasons for this:(1)FAeZn was able to utilize both ultraviolet and visible parts of the solar spectrum,and(2)its BrunauereEmmetteTeller surface area and porosity were significantly enhanced.This led to increased photon absorption and dye adsorption,thus exhibiting an energy-efficient performance.Therefore,FAeZn,partly derived from waste,can serve as a suitable material for environmental remediation and practical solar energy applications.展开更多
Tumor microenvironment(TME)with the particular features of severe hypoxia,insufficient endogenous H2O2,and overexpression of glutathione(GSH)markedly reduced the antitumor efficacy of monotherapy.Herein,a TME-responsi...Tumor microenvironment(TME)with the particular features of severe hypoxia,insufficient endogenous H2O2,and overexpression of glutathione(GSH)markedly reduced the antitumor efficacy of monotherapy.Herein,a TME-responsive multifunctional nanoplatform(Bi2S3@Bi@PDA-HA/Art NRs)was presented for synergistic photothermal therapy(PTT),chemodynamic therapy(CDT),and photodynamic therapy(PDT)to achieve better therapeutic outcomes.The Z-scheme heterostructured bismuth sulfide@bismuth nanorods(Bi2S3@Bi NRs)guaranteed excellent photothermal performance of the nanoplatform.Moreover,its ability to produce O2 and reactive oxygen species(ROS)synchronously could relieve tumor hypoxia and improve PDT outcomes.The densely coated polydopamine/ammonium bicarbonate(PDA/ABC)and hyaluronic acid(HA)layers on the surface of the nanoplatform enhanced the cancer-targeting capacity and induced the acidic TME-triggered in situ“bomb-like”release of Art.The CDT treatment was achieved by activating the released Art through intracellular Fe2+ions in an H2O2-independent manner.Furthermore,decreasing the glutathione peroxidase 4(GPX4)levels by Art could also increase the PDT efficiency of Bi2S3@Bi NRs.Owing to the synergistic effect,this nanoplatform displayed improved antitumor efficacy with minimal toxicity both in vitro and in vivo.Our design sheds light on the application of phototherapy combined with the traditional Chinese medicine monomer-artesunate in treating the hypoxic tumor.展开更多
The ever-increasing quantity of spent lithium-ion batteries(LIBs)is both a potential environmental pollutant and a valuable resource.The spent LIBs recycling mainly aimed at the separation of valuable elements.Some is...The ever-increasing quantity of spent lithium-ion batteries(LIBs)is both a potential environmental pollutant and a valuable resource.The spent LIBs recycling mainly aimed at the separation of valuable elements.Some issues still exist in these processes such as high energy consumption and complex separation procedures.This study avoided element separation and proposed a facile approach to transform spent LiCoO_(2) electrode into a lithium(Li)-doped graphitic carbon nitride(g-C_(3)N_(4))/Co_(3)O_(4) composite photocatalyst through one-pot in situ thermal reduction.During the thermal process,melamine served as the reductant for LiCoO_(2) decomposition and the raw material for g-C_(3)N_(4) production.Li was in situ doped in g-C_(3)N_(4) and the generated Co_(3)O_(4) was in situ integrated,forming a Li-doped g-C_(3)N_(4)/Co_(3)O_(4) composite photocatalyst.This special composite exhibited an enhanced photocatalytic performance,and its photocatalytic H2 production and RhB degradation rates were 8.7 and 6.8 times higher than those of g-C_(3)N_(4).The experiments combined with DFT calculation revealed that such enhanced photocatalytic efficiency was ascribed to the synergy effect of Li doping and Co_(3)O_(4) integrating,which extended the visible light absorption(450-900 nm)and facilitated the charge transfer and separation.This study transforms waste into a high-efficient catalyst,realizing high-valued utilization of waste and environmental protection.展开更多
The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The ...The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.展开更多
基金supported by National Natural Science Foundation of China(21975110 and 22279143)support from Taishan Youth Scholar Program of Shandong Province.
文摘In the midst of the rapid advancement of photocatalysis,direct Z-scheme heterojunction photocatalysts have emerged as a powerful solution to address environmental challenges and the looming energy crisis.The precise engineering of direct Z-scheme heterojunction photocatalysts proves highly beneficial in optimizing their elec-tronic structure,ultimately enhancing their photocatalytic performance.Notably,graphitic carbon nitride(g-C_(3)N_(4))has recently gained recognition as a leading candidate for the creation of direct Z-scheme heterojunctions,owing to its favorable attributes such as a moderate band-gap(2.7 eV),high reduction potential and abundant active sites.In this review,we offer a concise overview of the fundamental principles and recent advancements in g-C_(3)N_(4)-based direct Z-scheme photocatalytic systems.Furthermore,we delve into the various practical applica-tions of g-C_(3)N_(4)-based direct Z-scheme photocatalysts,specifically in the realms of energy conversion and envi-ronmental remediation.These applications include the removal of contaminant pollutants through photocatalytic degradation,water splitting(comprising H_(2)-generation,O_(2)-evolution,and overall water splitting),and CO_(2)reduction.Additionally,we present comprehensive characterization methods and strategies aimed at further enhancing the photocatalytic activity of g-C_(3)N_(4)-based direct Z-scheme photocatalytic systems.To conclude,this review offers summarizing insights and a brief discussion on future challenges and prospects pertaining to g-C_(3)N_(4)-based direct Z-scheme photocatalysts.We believe that this review will inspire continued exploration and foster a deeper understanding of the groundbreaking possibilities within photocatalytic activity.This also provides valuable guidance for the design and construction of innovative direct Z-scheme photocatalysts.
基金supported by the National Key R&D Program of China(2021YFA1502100 and 2022YFE0114800)the National Natural Science Foundation of China(22372035,22302039 and 22311540011).
文摘Photocatalytic water splitting by semiconductors is a promising technology to produce clean H_(2) fuel,but the efficiency is restrained seriously by the high overpotential of the H_(2)-evolution reaction together with the high recombination rate of photoinduced charges.To enhance H_(2) production,it is highly desirable yet challenging to explore an efficient reductive cocatalyst and place it precisely on the right sites of the photocatalyst surface to work the proton reduction reaction exclusively.Herein,the metalloid NixP cocatalyst is exactly positioned on the Z-scheme Cd_(0.5)Zn_(0.5)S/NiTiO_(3)(CZS/NTO)heterostructure through a facile photodeposition strategy,which renders the cocatalyst form solely at the electron-collecting locations.It is revealed that the directional transfer of photoexcited electrons from Cd_(0.5)Zn_(0.5)S to Ni_(x)P suppresses the quenching of charge carriers.Under visible light,the CZS/NTO hybrid loaded with the Ni_(x)P cocatalyst exhibits an optimal H_(2) yield rate of 1103μmol h^(-1)(i.e.,27.57 mmol h^(-1)g^(-1)),which is about twofold of pristine CZS/NTO and comparable to the counterpart deposited with the Pt cocatalyst.Besides,the high apparent quantum yield(AQY)of 56%is reached at 400 nm.Further,the mechanisms of the cocatalyst formation and the H2 generation reaction are discussed in detail.
基金supported primarily by the National Natural Science Foundation of China(Contract No.21975245,51972300,62274155,and U20A20206)the National Key Research and Development Program of China(Grant No.2018YFE0204000)+2 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDB43000000)the National Natural Science Foundation of China under Grant No.62175231.Prof.Kong Liu appreciates the support from the Youth Innovation Promotion Association,the Chinese Academy of Sciences(No.2020114)the Beijing Nova Program(No.2020117).
文摘Graphitic carbon nitride(g-C_(3)N_(4))has been extensively doped with alkali metals to enlarge photocatalytic output,in which cesium(Cs)doping is predicted to be the most efficient.Nevertheless,the sluggish diffusion and doping kinetics of precursors with high melting points,along with imprecise regulation,have raised the debate on whether Cs doping could make sense.For this matter,we attempt to confirm the positive effects of Cs doping on multifunctional photocatalysis by first using cesium acetate with the character of easy manipulation.The optimized Csdoped g-C_(3)N_(4)(CCN)shows a 41.6-fold increase in visible-light-driven hydrogen evolution reaction(HER)compared to pure g-C_(3)N_(4) and impressive degradation capability,especially with 77%refractory tetracycline and almost 100%rhodamine B degradedwithin an hour.The penetration ofCs+is demonstrated to be a mode of interlayer doping,and Cs–N bonds(especially with sp^(2) pyridine N in C═N–C),along with robust chemical interaction and electron exchange,are fabricated.This atomic configuration triggers the broadened spectral response,the improved charge migration,and the activated photocatalytic capacity.Furthermore,we evaluate the CCN/cadmium sulfide hybrid as a Z-scheme configuration,promoting the visible HER yield to 9.02 mmol g^(−1) h^(−1),which is the highest ever reported among all CCN systems.This work adds to the rapidly expanding field of manipulation strategies and supports further development of mediating served for photocatalysis.
基金supported by Russian Science Foundation (No.#21-73-10235)
文摘Extensive work on a Cu-modified TiO_(2) photocatalyst for CO_(2) reduction under visible light irradiation was conducted. The structure of the copper cocatalyst was established using UV-vis diff use refl ectance spectroscopy, high-resolution transmis- sion electron microscopy, X-ray absorption spectroscopy, and X-ray photoelectron spectroscopy. It was found that copper exists in different states (Cu 0 , Cu^(+) , and Cu^(2+) ), the content of which depends on the TiO_(2) calcination temperature and copper loading. The optimum composition of the cocatalyst has a photocatalyst based on TiO_(2) calcined at 700℃ and modified with 5 wt% copper, the activity of which is 22 μmol/(h·g cat ) (409 nm). Analysis of the photocatalysts after the photocatalytic reaction disclosed that the copper metal on the surface of the calcined TiO_(2) was gradually converted into Cu_(2) O during the photocatalytic reaction. Meanwhile, the metallic copper on the surface of the noncalcined TiO_(2) did not undergo any trans- formation during the reaction.
文摘This study focused on the development and characterization of TiO<sub>2</sub>-PES composite fibers with varying TiO<sub>2</sub> loading amounts using a phase inversion process. The resulting composite fibers exhibited a sponge-like structure with embedded TiO<sub>2</sub> nanoparticles within a polymer matrix. Their photocatalytic performance for ammonia removal from aqueous solutions under UV-A light exposure was thoroughly investigated. The findings revealed that PeTi8 composite fibers displayed superior adsorption capacity compared to other samples. Moreover, the study explored the impact of pH, light intensity, and catalyst dosage on the photocatalytic degradation of ammonia. Adsorption equilibrium isotherms closely followed the Langmuir model, with the results indicating a correlation between qm values of 2.49 mg/g and the porous structure of the adsorbents. The research underscored the efficacy of TiO<sub>2</sub> composite fibers in the photocatalytic removal of aqueous under UV-A light. Notably, increasing the distance between the photocatalyst and the light source resulted in de-creased hydroxyl radical concentration, influencing photocatalytic efficiency. These findings contribute to our understanding of TiO<sub>2</sub> composite fibers as promising photocatalysts for ammonia removal in water treatment applications.
基金This work was supported by the National Natural Science Foundation of China(Nos.21975190,21871215,21573166,and 21271146)the Science and Technology Planning Project of Shenzhen Municipality(No.JCYJ20180302153921190)the Fund for Innovative Research Groups of Hubei Province(No.2014CFA007),China.
文摘It is highly desirable to simulate natural photosynthesis by using sunlight to drive the overall water splitting without using external bias and sacrificial agent.Herein,few-layer monoclinic BiVO4 nanosheets(BVNS)with a thickness of(∼)4.3 nm,exposed(010)facets and abundant oxygen vacancies are fabricated using graphene oxide dots as templating reagent.After decorating with asymmetric chromium porphyrin derivative bearing one benzoic acid and three phenyls as meso-position substituents(chromium-5-(4-carboxyphenyl)-10,15,20-triphenylporphrin,CrmTPP)and PtOx cocatalyst,the obtained two-dimensional(2D)hybrid nanocomposite(BVNS/CrmTPP/Pt)with an optimal component ratio delivers a robust overall water splitting performance with a relatively high apparent quantum yield(8.67%)at 400 nm monochromatic light.The ultrathin structure and widely distributed oxygen vacancies on the exposed(010)facets of BVNS not only endow strong and intimate contact with the decorated CrmTPP molecules to promote a two-step excitation Z-scheme charge transfer mechanism for preserving the high redox ability of the photogenerated charge carriers,but also alleviate their recombination,and thus causing the robust overall water splitting performance of the 2D hybrid nanocomposites.The present results provide a novel strategy to construct highly efficient artificial photosynthetic system for overall water splitting.
基金Project supported by the Science and Engineering Research Board(SERB),Government of India(EMR/2016/001811,EMR/2016/000083)。
文摘The major findings in this report are(ⅰ)development of nanocomposite photocatalyst working through Z-scheme charge transfer pathway across the heterojunction,(ⅱ)utilization of direct sunlight as the photo-source,and(ⅲ)prospect of ligand-hole in photocatalysis through enhanced sub-band gap absorption,The photocatalysts,namely LaNiO_(3),g-C_(3)N_(4) and LaNiO_(3)/g-C_(3)N_(4) nanocomposites were synthesized via facile route and were characterized for their structure,morphology,microstructure,texture,elemental mapping and surface oxidation states by using several physicochemical techniques.The photocatalytic performance of the nanocomposite was tested through the degradation of hazardous azo dye pollutants,namely reactive black 5 and methylene blue as well as the colorless antibiotic-pollutant tetracycline hydrochloride in aqueous solution in presence of natural sunlight with excellent recycling activity.The 10%LaNiO_(3)/g-C_(3)N_(4) nanocomposite sample shows the best catalytic activity,degrading respectively 94%,98.6%and 88.1%of reactive black 5,methylene blue and tetracycline hydrochloride in60,180 and 120 min.The photocatalytic activity of the nanocomposite phase is several times superior to that of the pure phases.The improvements of photocatalytic activity of g-C_(3)N_(4) in the nanocomposite have been rationalized through the construction of direct Z-scheme heterojunction and suppression of electron-hole pair recombination efficiency.The enhanced photo-absorption of the nanocomposite can possibly be related to sub-bandgap absorption,which is associated to the midgap state originating from ligand-hole formation or defects in the structure.The photodegradation process is mediated through the formation of super oxide radical(O_(2))and hole(h^(+))as the main responsible species.
基金supported by the Natural Science Foundation of Shandong Province of China(ZR2019MB006)National Natural Science Foundation of China(21303232)Natural Science Foundation of Guangdong Province(2018A030313460).
文摘With continuous consumption of nonrenewable energy,solar energy has been predicted to play an essential role in meeting the energy demands and miti gating environmental issues in the future.Despite being green,clean and pollution-free energy,solar energy cannot be adopted directly as it cannot provide sufficiently high energy density to work in the absence of machinery.Thus,it is necessary to develop an effective strategy to convert and store solar energy into chemical energy to achieve social sustainable development using solar energy as the main power source.Photocatalysis,in which semi conductor photocatalysts play a key role,is one of the most promising can didates for realising the effective utilisation of sunlight in a green,low-cost and environmentally friendly method.The photocatalytic efficiency of photo catalysts is considerably influenced by their compositions.Among the various heterostructures,Z-scheme heterojunction is one of the most interesting ar chitecture due to its outstanding performance and excellent artificial imitation of photosynthesis.Z-scheme photocatalysts have attracted considerable at tention in the past few decades.Herein,we review contemporary Z-scheme systems,with a particular focus on mechanistic breakthroughs,and highlight current state-of-the-art systems.Z-type photocatalysts are classified as tradi tional,all-solid-state,direct Z-schemes and S-scheme photocatalysts.The morphology,characterisation and working mechanism of each type of Z-scheme are discussed in detail.Furthermore,the applications of Z-scheme in photoelectrochemical water splitting,nitrogen fixation,pollutant degrada tion and carbon dioxide reduction are illustrated.Finally,we outline the main challenges and potential advances in Z-scheme architectures,as well as their future development directions.
基金supported by National Natural Science Foundation of China(21776118,21808090)Natural Science Foundation of Jiangsu Province(BK20190981)+3 种基金Jiangsu Fund for Distinguished Young Scientists(BK20190045)China Postdoctoral Science Foundation(2019M661765)High-tech Research Key laboratory of Zhenjiang(SS2018002)A Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions,the high-performance computing platform of Jiangsu University。
文摘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.
基金the Independent Cultivation Program of Innovation Team of Ji’nan City(No.2019GXRC011)the National Natural Science Foundation of China(Nos.21707043 and 51908242)the Natural Science Foundation of Shandong Province(No.ZR2017BEE005)。
文摘Improving the separation efficiency of photogenerated carriers and broadening the light absorption range of the photocatalyst are two important factors for improving the performance of the photocatalyst.In this paper,a new and efficient Z-scheme Cd S/iron phthalocyanine(Cd S/Fe Pc)core-shell nanostructure composite material is prepared by a simple solid-phase reaction method.There are two key points in the preparation of composite materials:one is that hydrogen bonding energy is closely connected with Fe Pc,another is that Fe Pc can be uniformly assembled on Cd S nanoparticles.The photocatalytic hydrogen evolution(PHE)of the Cd S/Fe Pc nanocomposite(73.01μmol/h)is 2.6 times higher than that of pure Cd S(26.67μmol/h).In addition,after 4 photocatalytic cycles,the PHE of the Cd S/Fe Pc composite is still 92.3%of the first cycle.There are three reasons for this situation:(1)The Z-scheme heterojunction is formed to improve the separation efficiency of photogenerated carriers;(2)Fe Pc expands the visible light absorption range of Cd S;(3)The large core-shell contact area is favorable for the separation of photo-induced carriers at the interfaces.This research is conducive to the further development of new photocatalytic materials with high efficiency,low cost and simple preparation.
基金the financial support by the National Natural Science Foundation of China (grant no. 51272107 and 51372118)the Doctor Discipline Special Research Foundation of Chinese Ministry of Education (grant no. 20133219110015)
文摘In this study, the Ag/Ag Cl/WO3 plasmonic Z-scheme photocatalysts with different contents of Ag/Ag Cl nanoparticles(NPs) were prepared through a facile ultrasonic precipitation method in geothermal water,wherein the geothermal water served as the chlorine source. Then the photocatalytic activity was investigated by degradation of 4-Aminobenzoic acid(4-ABA) under visible-light irradiation. It was found that the as-prepared 50 wt% Ag/Ag Cl/WO3 photocatalyst showed the highest photocatalytic efficiency with 25.12 and 3.53 times higher than those of pure WO3 and Ag/Ag Cl, respectively. The active species trapping experiments indicated that h+and ·O2-were key factors in 4-ABA photodegradation process. The possible plasmonic Z-scheme photocatalytic mechanism of photocatalytic reaction for 4-ABA degradation was proposed based on systematical characterizations. We hope this paper could give new ideas for further exploiting geothermal energy to design and fabricate highly efficient visible-light-driven photocatalysts for environmental remediation.
基金support of this research by the National Natural Science Foundation of China(21871078)the Natural Science Foundation of Heilongjiang Province(JQ2019B001 and B2018010)+3 种基金the Heilongjiang Postdoctoral Startup Fund(LBH-Q14135)the Heilongjiang University Science Fund for Distinguished Young Scholars(JCL201802)the Heilongjiang Provincial Institutions of Higher Learning Basic Research Funds Basic Research Projects(KJCX201909)the Heilongjiang Touyan Innovation Team Program.
文摘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.
基金We gratefully acknowledge the support of this research by the National Natural Science Foundation of China(52172206,21871078)the Heilongjiang Province Natural Science Foundation of China(JQ2019B001)+4 种基金the Shandong Province Natural Science Foundation(ZR2021MB016)the Heilongjiang Provincial Institutions of Higher Learning Basic Research Funds Basic Research Projects(2021-KYYWF-0007)the Heilongjiang Postdoctoral Startup Fund(LBH-Q14135)the Heilongjiang University Science Fund for Distinguished Young Scholars(JCL201802)the Development plan of Youth Innovation Team in Colleges and Universities of Shandong Province.
文摘Photocatalysis is an effective way to solve the problems of environmental pollution and energy shortage.Numerous photocatalysts have been developed and various strategies have been proposed to improve the photocatalytic performance.Among them,Bi-based photocatalysts have become one of the most popular research topics due to their suitable band gaps,unique layered structures,and physicochemical properties.In this review,Bi-based photocatalysts(BiOX,BiVO_(4),Bi_(2)S_(3),Bi_(2)MoO_(6),and other Bi-based photocatalysts)have been summarized in the field of photocatalysis,including their applications of the removal of organic pollutants,hydrogen production,oxygen production etc.The preparation strategies on how to improve the photocatalytic performance and the possible photocatalytic mechanism are also summarized,which could supply new insights for fabricating high-efficient Bi-based photocatalysts.Finally,we summarize the current challenges and make a reasonable outlook on the future development direction of Bi-based photocatalysts.
基金support from the National Key R&D Plan Project(No.2022YFA1505000)Prospective Basic Research Projects of CNPC(Nos.2021DQ03(2022Z-29)+4 种基金2022DJ5406,2022DJ5407,2022DJ5408,2022DJ4507,and TGRI-2021-1)the Natural Science Foundation of Shaanxi Province(No.2022JQ-078)the Natural Science Foundation of China(No.52302308)the Outstanding Youth Science Foundation Project of the National Natural Science Foundation of China(Overseas)(No.GYKP033)the Qinchuangyuan Cited High-Level Innovative and Entrepreneurial Talents Project(No.QCYRCXM-2022-143).
文摘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.
基金the Opening Project of Key Laboratory of Green Catalysis of Higher Education Institutes of Sichuan(Grant number:LZJ2101)the Fundamental Research Funds of China West Normal University(Grant number:19D038).
文摘Polyimide(PI) is an organic polymer material with good stability and diverse sources that has attracted widespread attention in the field of photocatalysis. In this study, a series of PI photocatalysts were synthesized by a thermal polymerization approach using pyromellitic dianhydride(PMDA) and various diamine monomers(melamine(MA), 4,4′-oxydianiline, and melem) as the precursors as well as different heating rates. The effects of the diamine precursor and heating rate on the structure, composition, morphology, and optical properties of the as-prepared PI materials were systematically investigated by various characterization techniques. The selective photo-oxidation of benzylamine was used as a model reaction to evaluate the photocatalytic activities of the resulting PI samples for the oxidation of amines to imines. The results revealed that the PI sample prepared using MA and PMDA as the precursors and a heating rate of 7 ℃/min(MA-PI-7) exhibited the best catalytic performance, with 98% benzylamine conversion and 98% selectivity for N-benzylidene benzylamine after 4 h of irradiation. Several benzylamine derivatives and heterocyclic amines also underwent the photo-oxidation reaction over the MA-PI-7 catalyst to afford the corresponding imines with good activity. In addition, MA-PI-7 exhibited good stability over four successive photocatalytic cycles.
文摘Treating waste with a waste material using freely available solar energy is the most effective way towards sustainable future.In this study,a novel photocatalyst,partly derived from waste material from the coal industry,was developed.Fly ash hybridized with ZnO(FAeZn)was synthesized as a potential photocatalyst for dye discoloration.The synthesized photocatalyst was characterized by X-ray diffraction,scanning electron microscopy,transmission electron microscopy,and ultravioletevisible/near infra-red spectroscopy.The photocatalytic activity was examined with the discoloration of methylene blue used as synthetic dye wastewater.All the experiments were performed in direct sunlight.The photocatalytic performance of FAeZn was found to be better than that of ZnO and the conventionally popular TiO2.The LangmuireHinshelwood model rate constant values of ZnO,TiO2,and FAeZn were found to be 0.016 min1,0.017 min1,and 0.020 min1,respectively.There were two reasons for this:(1)FAeZn was able to utilize both ultraviolet and visible parts of the solar spectrum,and(2)its BrunauereEmmetteTeller surface area and porosity were significantly enhanced.This led to increased photon absorption and dye adsorption,thus exhibiting an energy-efficient performance.Therefore,FAeZn,partly derived from waste,can serve as a suitable material for environmental remediation and practical solar energy applications.
基金Financial support was provided by the National Natural Science Foundation of China(grant no.21807024)the Youth Top-notch Talents Supporting Plan of Hebei Province(QNBJ19004)+4 种基金Scientific Research Foundation of Hebei Province for the Returned Overseas Chinese Scholars(C20220508)the Science and Technology Project of Hebei Education Department(no.ZD2021072)the Central Guidance on Local Science and Technology Development Fund of Hebei Province(226Z2601G)Science Fun for Creative Research Groups of Natural Science Foundation of Hebei Province(no.H2020206474)supported by the Postdoctoral Fund of Hebei Medical University.
文摘Tumor microenvironment(TME)with the particular features of severe hypoxia,insufficient endogenous H2O2,and overexpression of glutathione(GSH)markedly reduced the antitumor efficacy of monotherapy.Herein,a TME-responsive multifunctional nanoplatform(Bi2S3@Bi@PDA-HA/Art NRs)was presented for synergistic photothermal therapy(PTT),chemodynamic therapy(CDT),and photodynamic therapy(PDT)to achieve better therapeutic outcomes.The Z-scheme heterostructured bismuth sulfide@bismuth nanorods(Bi2S3@Bi NRs)guaranteed excellent photothermal performance of the nanoplatform.Moreover,its ability to produce O2 and reactive oxygen species(ROS)synchronously could relieve tumor hypoxia and improve PDT outcomes.The densely coated polydopamine/ammonium bicarbonate(PDA/ABC)and hyaluronic acid(HA)layers on the surface of the nanoplatform enhanced the cancer-targeting capacity and induced the acidic TME-triggered in situ“bomb-like”release of Art.The CDT treatment was achieved by activating the released Art through intracellular Fe2+ions in an H2O2-independent manner.Furthermore,decreasing the glutathione peroxidase 4(GPX4)levels by Art could also increase the PDT efficiency of Bi2S3@Bi NRs.Owing to the synergistic effect,this nanoplatform displayed improved antitumor efficacy with minimal toxicity both in vitro and in vivo.Our design sheds light on the application of phototherapy combined with the traditional Chinese medicine monomer-artesunate in treating the hypoxic tumor.
基金supported by the National Natural Science Foundation of China(51534005)Postdoctoral Innovative Talent Support Program(BX20190200)China Postdoctoral Science Foundation(2020M671129)。
文摘The ever-increasing quantity of spent lithium-ion batteries(LIBs)is both a potential environmental pollutant and a valuable resource.The spent LIBs recycling mainly aimed at the separation of valuable elements.Some issues still exist in these processes such as high energy consumption and complex separation procedures.This study avoided element separation and proposed a facile approach to transform spent LiCoO_(2) electrode into a lithium(Li)-doped graphitic carbon nitride(g-C_(3)N_(4))/Co_(3)O_(4) composite photocatalyst through one-pot in situ thermal reduction.During the thermal process,melamine served as the reductant for LiCoO_(2) decomposition and the raw material for g-C_(3)N_(4) production.Li was in situ doped in g-C_(3)N_(4) and the generated Co_(3)O_(4) was in situ integrated,forming a Li-doped g-C_(3)N_(4)/Co_(3)O_(4) composite photocatalyst.This special composite exhibited an enhanced photocatalytic performance,and its photocatalytic H2 production and RhB degradation rates were 8.7 and 6.8 times higher than those of g-C_(3)N_(4).The experiments combined with DFT calculation revealed that such enhanced photocatalytic efficiency was ascribed to the synergy effect of Li doping and Co_(3)O_(4) integrating,which extended the visible light absorption(450-900 nm)and facilitated the charge transfer and separation.This study transforms waste into a high-efficient catalyst,realizing high-valued utilization of waste and environmental protection.
基金Taishan Scholars Program of Shandong Province,Grant/Award Number:tsqn201812068Higher School Youth Innovation Team of Shandong Province,Grant/Award Number:2019KJA013+1 种基金The Opening Fund of State Key Laboratory of Heavy Oil Processing,Grant/Award Number:SKLOP202002006National Natural Science Foundation of China,Grant/Award Number:51872173。
文摘The reduction of molecular nitrogen(N_(2))to ammonia(NH_(3))under mild conditions is one of the most promising studies in the energy field due to the important role of NH_(3)in modern industry,production,and life.The photocatalytic reduction of N_(2)is expected to achieve clean and sustainable NH_(3)production by using clean solar energy.To date,the new photocatalysts for photocatalytic reduction of N_(2)to NH_(3)at room temperature and atmospheric pressure have not been fully developed.The major challenge is to achieve high light-absorption efficiency,conversion efficiency,and stability of photocatalysts.Herein,the methods for measuring produced NH_(3)are compared,and the problems related to possible NH_(3)pollution in photocatalytic systems are mentioned to provide accurate ideas for measuring photocatalytic efficiency.The recent progress of nitrogen reduction reaction(NRR)photocatalysts at ambient temperature and pressure is summarized by introducing charge transfer,migration,and separation in photocatalytic NRR,which provides a guidance for the selection of future photocatalyst.More importantly,we introduce the latest research strategies of photocatalysts in detail,which can guide the preparation and design of photocatalysts with high NRR activity.