The effect of superheated steam(SHS)treatment on the quality characteristics of rape bee pollen were studied,and the efficiency of inactivation and inhibition of lipid oxidation were analyzed to investigate the differ...The effect of superheated steam(SHS)treatment on the quality characteristics of rape bee pollen were studied,and the efficiency of inactivation and inhibition of lipid oxidation were analyzed to investigate the differences between SHS and cobalt-60 isotope(^(60)Co)radiation treatment.The number of total plate count(TPC)and mold colonies(MC)remained within the limits of the standards after SHS treatment at 140℃for 2 min.Neither TPC nor MC were detected after^(60)Co irradiation.Peroxidase(POD)and polyphenol oxidase(PPO)activities significantly decreased with increasing temperature and duration of SHS,while^(60)Co radiation completely inactivated PPO.Compared to^(60)Co radiation,SHS treatment inhibited the deterioration of rape bee pollen by avoiding hydroperoxide production and lipid oxidation due to lack of oxygen.These results suggested SHS under 140℃for 2 min was the most suitable to inactivate the microorganisms and enzymes in rape bee pollen with minimal lipid oxidation.展开更多
Low-valent sulfur oxy-acid salts(LVSOs)represent a category of oxygen-containing salts characterized by their potent reducing capabilities.Notably,sulfite,dithionite,and thiosulfate are prevalent reducing agents that ...Low-valent sulfur oxy-acid salts(LVSOs)represent a category of oxygen-containing salts characterized by their potent reducing capabilities.Notably,sulfite,dithionite,and thiosulfate are prevalent reducing agents that are readily available,cost-effective,and exhibit minimal ecological toxicity.These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants,which makes them widely used in advanced oxidation processes(AOPs)and advanced reduction processes(ARPs).This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs,alongside an examination of the fundamental principles governing the generation of active species within these processes.LVSOs fulfill three primary functions in AOPs:Serving as sources of reactive oxygen species(ROS),auxiliary agents,and activators.Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs,in conjunction with metal ions,metal oxides,ultraviolet light(UV),and ozone,produce potent oxidizing agents in both homogeneous and heterogeneous systems.Regarding ARPs,this review delineates the mechanisms by which LVSOs generate strong reducing agents,including hydrated electrons,hydrogen radicals,and sulfite radicals,under UV irradiation,while also exploring the interactions between these reductants and pollutants.The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.展开更多
Hydrogen peroxide(H_(2)O_(2))electrosynthesis via two-electron oxygen reduction reaction(2e-ORR)is a promising alternative for the energy-intensive anthraquinone process.However,the instability of the catalytic metal ...Hydrogen peroxide(H_(2)O_(2))electrosynthesis via two-electron oxygen reduction reaction(2e-ORR)is a promising alternative for the energy-intensive anthraquinone process.However,the instability of the catalytic metal sites in the state-of-the-art metal single-atom catalysts(M-SACs)hinders their further industrial applications,and the high potential and valueless oxygen product of the conventional anodic oxygen evolution reaction(OER)further limit the economic efficiency of this technology.To address this,a dynamically local structure reconstruction strategy is proposed to in situ transfer the active sites from unstable metal sites to the stable surrounding carbon sites for efficient and durable 2e^(-)ORR electrocatalysis.For the as-designed Mn-N_(3)O-C catalyst,by reconstructing Mn sites into Mn(^(*)OH),the Mn sites were passivated and carbon sites adjacent to the O atom were verified to be the actual active sites by in situ characterization and theoretical calculation.Consequently,Mn-N_(3)O-C exhibited>80%Faradaic efficiency and superior long-term durability over 100 h for H_(2)O_(2)electrosynthesis at~120 mA cm^(-2).In addition,coupling anodic ethylene glycol oxidation reaction(EGOR)further improves the efficiency and economic viability of the H_(2)O_(2)electrosynthesis system.This two-pronged strategy thus opens up a new opportunity for the development of stable H_(2)O_(2)electrosynthesis with low energy consumption and superior economic performance.展开更多
Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance ...Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.展开更多
Simultaneously inducing dual built-in electric fields(EFs)both within a single component and at the heterojunction interface creates a dual-driving force that is crucial for promoting spatial charge separation.This is...Simultaneously inducing dual built-in electric fields(EFs)both within a single component and at the heterojunction interface creates a dual-driving force that is crucial for promoting spatial charge separation.This is particularly significant in challenging coupled systems,such as CO_(2)photoreduction integrated with selective oxidation of toluene to benzaldehyde.However,developing such a system is quite challenging and often requires a precise design and engineering.Herein,we demonstrate a unique Ni-CdS@Ni(OH)_(2)heterojunction synthesized via an in-situ self-assembly method.Comprehensive mechanistic and theoretical investigations reveal that the NiCdS@Ni(OH)_(2)heterojunction induces dual electric fields(EFs):an intrinsic polarized electric-field within the CdS lattice from Ni doping and an interfacial electric-field from the growth of ultrathin nanosheets of Ni(OH)_(2)on NiCdS nanorods,enabling efficient spatial charge separation and enhanced redox potential.As proof of concept,the Ni-CdS@Ni(OH)_(2)heterojunction simultaneously exhibits outstanding bifunctional photocatalytic performance,producing CO at a rate of 427μmol g^(-1)h^(-1)and selectively oxidizing toluene to benzaldehyde at a rate of 1476μmol g^(-1)h^(-1)with a selectivity exceeding 85%.This work offers a promising strategy to optimize the utilization of photogenerated carriers in heterojunction photocatalysts,advancing synergistic photocatalytic redox systems.展开更多
Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocat...Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.展开更多
Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat micr...Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat microplastic waste and CO_(2)by using environmentally friendly and efficient technologies.In this work,we developed an efficient photoelectrocatalytic system composed of Ni single atoms(Ni SAs)supported by P,N-doped amorphous NiFe_(2)O_(4)(Ni SAs/A-P-N-NFO)as anode and Ag nanoparticles(Ag NPs)supported by CuO/Cu_(2)O nanocubes(Ag NPs@CuO/Cu_(2)O NCs)as cathode for microplastic oxidation and CO_(2)reduction.The Ni SAs/A-P-N-NFO was synthesized by calcination-H_(2)reduction method,and it achieved a Faraday efficiency of 93%for the oxidation reaction of poly(ethylene terephthalate)(PET)solution under AM 1.5 G light.As a photocathode,the synthesized Ag NPs@CuO/Cu_(2)O NCs was utilized to reduce CO_(2)to ethylene and CO at 1.5 V vs.RHE with selectivity of 42%and 55%,respectively.This work shows that the photoelectrocatalysis,as an environmentally friendly technology,is a feasible strategy for reducing the environmental and biological hazards of light plastics,as well as for efficient CO_(2)reduction.展开更多
Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.展开更多
Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly ...Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.展开更多
Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction(ORR),whereas the...Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction(ORR),whereas the investigation on the electrocatalytic performance of perovskite oxides toward the two-electron ORR to H_(2)O_(2)production remains very limited.Herein,a facile synthetic method has been developed to prepare La_(2)Sn_(2)O_(7)@La-doped ZnSnO_(3)heterostructures comprising of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).The optimal La_(2)Sn_(2)O_(7)@Ladoped ZnSnO_(3)heterostructures catalyst exhibits a significantly improved two-electron ORR performance to H_(2)O_(2)production with onset potential of 0.77 V and large current density of 2.51 m A.cm^(-2)at 0.1 V compared to ZnSnO_(3)(0.75 V,1.80 m A.cm^(-2),0.11 m A) as well as maintains high H_(2)O_(2)selectivity of 80%,which has been theoretically demonstrated to be contributed to the synergistic effect of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).Moreover,high H_(2)O_(2)yield rate of 2.9 m M.h^(-1)at 0.1 V can be achieved with a superior turnover frequency(TOF) of3.31 × 10^(-2)s^(-1)compared to the ZnSnO_(3)catalyst(2.10 × 10^(-2)s^(-1)).This work reveals the great potential of perovskite oxide as promising candidates for the environmentally friendly synthesis of hydrogen peroxide.展开更多
The development of efficient and durable electrocatalysts for oxygen reduction reaction(ORR)holds a pivotal significance in the successful commercialization of proton exchange membrane fuel cells(PEMFCs)but is still c...The development of efficient and durable electrocatalysts for oxygen reduction reaction(ORR)holds a pivotal significance in the successful commercialization of proton exchange membrane fuel cells(PEMFCs)but is still challenging.Herein,we report a worm-liked PtCu nanocrystals dispersed on nitrogen-doped carbon hollow microspheres(Pt_(0.38)Cu_(0.62)/N-HCS).Benefiting from its structural and compositional advantages,the resulting Pt_(0.38)Cu_(0.62)/N-HCS catalyst delivers exceptional electrocatalytic activity for ORR,with a half-wave potential(E_(1/2))of 0.837 V,a mass activity of 0.672 A mgPt^(-1),and a Tafel slope of 50.66 mV dec^(-1),surpassing that of commercial Pt/C.Moreover,the Pt_(0.38)Cu_(0.62)/N-HCS follows the desired four-electron transfer mechanism throughout the ORR process,thereby displaying a high selectivity for direct reduction of O_(2)to H_(2)O.Remarkably,this catalyst also showcases high stability,with only a 25 mV drop in E_(1/2)after 10,000 cycles in an acidic electrolyte.Theoretical calculations elucidate the incorporation of Cu into Pt lattice induces compressive strain,which effectively tailors the d band center of Pt active sites and strengthens the surface chemisorption of O_(2)molecules on PtCu alloys.Consequently,the Pt_(0.38)Cu_(0.62)/N-HCS catalyst exhibits an improved ability to adsorb O_(2)molecules on its surface,accelerating the reaction kinetics of O_(2)conversion to*OOH.Additionally,Cu atoms,not only serving as sacrificial anode,undergo preferential oxidation during PEMFCs operation when compared to Pt,but also the stable Cu species in PtCu alloys contributes significantly to maintaining the strain effect,collectively enhancing both activity and durability.Overall,this research offers an effective and promising approach to enhance the activity and stability of Pt-based ORR electrocatalysts in PEMFCs.展开更多
Anaerobic digestion(AD),as an eco-friendly biological process,shows potential for the decomposition of leachate produced by waste incineration power plants.In this study,the effects of Fe oxides nano-modified pumice(F...Anaerobic digestion(AD),as an eco-friendly biological process,shows potential for the decomposition of leachate produced by waste incineration power plants.In this study,the effects of Fe oxides nano-modified pumice(FNP)were investigated on the fresh leachate AD process.Firstly,a simple hydrothermal method was used to prepare FNP,then introduced into the UASB reactor to evaluate its AD efficiency.Results showed that the inclusion of FNP could shorten the lag phase by 10 days compared to the control group.Furthermore,cumulative methane production in the FNP group was enhanced by 20.11%.Mechanistic studies suggested that hydrogenotrophic methanogenesis in the FNP group was more pronounced due to the influence of key enzymes(i.e.,dehydrogenase and coenzyme F420).Microbial community analysis demonstrated that FNP could enhance the abundance of Methanosarcina,Proteobacteria,Sytrophomonas,and Limnobacter,which might elevate enzyme activity involved in methane production.These findings suggest that FNP might mediate interspecies electron transfer among these microorganisms,which is essential for efficient leachate treatment.展开更多
The insufficient electrocatalytic activity and CO_(2)resistance hinder the application of cathode mate-rial for solid oxide fuel cells(SOFCs).In this study,we introduce a series of Pr-doped perovskite Bi_(0.8-x)Pr_(x)...The insufficient electrocatalytic activity and CO_(2)resistance hinder the application of cathode mate-rial for solid oxide fuel cells(SOFCs).In this study,we introduce a series of Pr-doped perovskite Bi_(0.8-x)Pr_(x)Ca_(0.2)FeO_(3-δ)(BPCF_(x),x=0,0.10,0.15,0.20)as candidate cathode materials,with a focus on its phase structure,oxygen desorption ability,catalytic activity,and electrochemical reduction kinetics.Among all the components,the Bi_(0.6)Pr_(0.2)Ca_(0.2)FeO_(3-δ)(BPCF0.20)catalyst shows impressive oxygen reduc-tion reaction(ORR)activity,with a low polarization resistance of 0.06Ωcm^(2)at 700℃and peak power density of 810 mW cm^(−2)at 800℃.Moreover,the BPCF0.20 cathode shows outstanding CO_(2)resistance in different CO_(2)concentrations(1%-10%)due to the larger average bond energy and higher relative acidity of Bi,Pr,and Fe ions.These findings demonstrate that BPCF_(x)are advanced cathode electrocatalysts for SOFCs.展开更多
The reduction of global carbon emissions and the achievement of carbon neutrality have become the focus of addressing climate change and global warming.Electrochemical CO_(2) reduction(CO_(2)RR),as a technology that c...The reduction of global carbon emissions and the achievement of carbon neutrality have become the focus of addressing climate change and global warming.Electrochemical CO_(2) reduction(CO_(2)RR),as a technology that can efficiently convert CO_(2) into value-added products,is receiving widespread attention.This article reviews the current research status of Cu/metal oxide heterostructures in the field of electrochemical reduction of CO_(2).The review first introduces the importance of electrochemical reduction of CO_(2) and the application potential of Cu/metal oxide heterostructures in this field.Subsequently,a comprehensive discussion is presented on the exploration of various Cu/metal oxide heterostructures and their corresponding structure-performance relationship,with particular emphasis on the catalysts'activity,selectivity,stability and the nature of active sites.Lastly,the review provides an overview of the current research challenges and future development trends in this field.展开更多
Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and ...Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and active catalyst for CO_(2)RR but suffers from structural reconstruction challenges.Hybrid organic/inorganic materials address these issues by offering customizable compositions and interfaces.Recently,Buonsanti’s team developed hybrid Cu@AlOx nanocrystals with tunable alumina shells via a colloidal atomic layer deposition approach,achieving stable and selective methane production during CO_(2)RR.Mechanistic studies reveal that the alumina shell stabilizes oxidized copper species through Cu^(2+)-O-Al motifs coordinated with AlO_(4) Lewis acid sites,reducing copper dissolution and structural reconstruction.This study provides key insights into the mechanism underlying stabilization,highlighting the critical role of Lewis acidity in preserving the structural integrity of the catalyst.This highlight review aims to inspire the development of other high-performance and stable catalysts through colloidal atomic layer deposition strategies.展开更多
Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoun...Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.展开更多
To improve the sludge conditioning efficiency without increasing the ozone dose,an in-situ sludge reduction process based on Mn^(2+)-catalytic ozonation conditioning was proposed.Using ozone conditioning alone as a co...To improve the sludge conditioning efficiency without increasing the ozone dose,an in-situ sludge reduction process based on Mn^(2+)-catalytic ozonation conditioning was proposed.Using ozone conditioning alone as a control,a lab-scale sequencing batch reactor coupled with ozonated sludge recycle was evaluated for its operating performance at an ozone dose of 75 mg O_(3)/g VSS and 1.5 mmol/L Mn^(2+)addition.The results showed a 39.4%reduction in MLSS and an observed sludge yield of 0.236 kg MLSS/kg COD for the O_(3)+Mn^(2+)group compared to the O_(3)group (15.3%and 0.292 kg MLSS/kg COD),accompanied by better COD,NH_(4)^(+)-N,TN and TP removal,improved effluent SS and limited impact on excess sludge properties.Subsequently,activity tests,BIOLOG ECO microplates and 16S rRNA sequencing were applied to elucidate the changing mechanisms of Mn^(2+)-catalytic ozonation related to microbial action:(1) Dehydrogenase activity reached a higher peak.(2) Microbial utilization of total carbon sources had an elevated effect,up to approximately 18%,and metabolic levels of six carbon sources were also increased,especially for sugars and amino acids most pronounced.(3) The abundance of Defluviicoccus under the phylum Proteobacteria was enhanced to 12.0%and dominated in the sludge,they had strong hydrolytic activity and metabolic capacity.Denitrifying bacteria of the genus Ferruginibacter also showed an abundance of 7.6%,they contributed to the solubilization and reduction of sludge biomass.These results could guide researchers to further reduce ozonation conditioning costs,improve sludge management and provide theoretical support.展开更多
Water scarcity is an escalating global crisis,posing a severe threat to populations worldwide.Consequently,exploring various materials to remove emerging contaminants from freshwater sources has garnered significant a...Water scarcity is an escalating global crisis,posing a severe threat to populations worldwide.Consequently,exploring various materials to remove emerging contaminants from freshwater sources has garnered significant attention.In this regard,single-atom catalysis(SACs) has emerged as a catalyst of scientific progress in water purification and treatment methodologies during recent decades.SACs exhibit exceptional catalytic activity,selectivity and stability,due to their near-perfect atom utilization,highly unsaturated coordination environment and uniform reaction centers.However,a comprehensive and critical review encompassing the successful integration of SACs into water purification processes needs to be completed.This review aims to accentuate recent trends by presenting the synthesis,structure,and environment and energy application-relevant properties of SACs.The results show that a comprehensive and multi-perspective summary of the advantages of SACs in environmental remediation can have significant benefits,such as fast kinetics,costeffectiveness,selectivity.The oxidation and reduction processes of SACs and functional SACs materials in water purification were emphasized.Furthermore,the last section is devoted to the current research gaps and further perspectives on the application of SACs in water treatment,which are summarized and analyzed.展开更多
N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher ...N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.展开更多
Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles...Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.展开更多
基金supported by National Natural Science Foundations of China(32472396,31871861 and 31501548)The Apicultural Industry Technology System(NCYTI-43-KXJ17)The Science and Technology Innovation Project of Chinese Academy of Agricultural Sciences(CAAS-ASTIP-2015-IAR)。
文摘The effect of superheated steam(SHS)treatment on the quality characteristics of rape bee pollen were studied,and the efficiency of inactivation and inhibition of lipid oxidation were analyzed to investigate the differences between SHS and cobalt-60 isotope(^(60)Co)radiation treatment.The number of total plate count(TPC)and mold colonies(MC)remained within the limits of the standards after SHS treatment at 140℃for 2 min.Neither TPC nor MC were detected after^(60)Co irradiation.Peroxidase(POD)and polyphenol oxidase(PPO)activities significantly decreased with increasing temperature and duration of SHS,while^(60)Co radiation completely inactivated PPO.Compared to^(60)Co radiation,SHS treatment inhibited the deterioration of rape bee pollen by avoiding hydroperoxide production and lipid oxidation due to lack of oxygen.These results suggested SHS under 140℃for 2 min was the most suitable to inactivate the microorganisms and enzymes in rape bee pollen with minimal lipid oxidation.
基金supported by Natural Science Foundation of China(Nos.52070133,42107073,42477075)Natural Science Foundation of Sichuan Province(No.2024NSFSC0130)+2 种基金the Sichuan Science and Technology Program(No.2024NSFTD0014)Key Laboratory of Jiangxi Province for Persistent Pollutants Prevention Control and Resource Reuse(No.2023SSY02061)Key R&D Program of Heilongjiang Province(No.2023ZX02C01)。
文摘Low-valent sulfur oxy-acid salts(LVSOs)represent a category of oxygen-containing salts characterized by their potent reducing capabilities.Notably,sulfite,dithionite,and thiosulfate are prevalent reducing agents that are readily available,cost-effective,and exhibit minimal ecological toxicity.These LVSOs have the ability to generate or promote the generation of strong oxidants or reductants,which makes them widely used in advanced oxidation processes(AOPs)and advanced reduction processes(ARPs).This article provides a comprehensive review of the recent advancements in AOPs and ARPs involving LVSOs,alongside an examination of the fundamental principles governing the generation of active species within these processes.LVSOs fulfill three primary functions in AOPs:Serving as sources of reactive oxygen species(ROS),auxiliary agents,and activators.Particular attention is devoted to elucidating the reaction mechanisms through which LVSOs,in conjunction with metal ions,metal oxides,ultraviolet light(UV),and ozone,produce potent oxidizing agents in both homogeneous and heterogeneous systems.Regarding ARPs,this review delineates the mechanisms by which LVSOs generate strong reducing agents,including hydrated electrons,hydrogen radicals,and sulfite radicals,under UV irradiation,while also exploring the interactions between these reductants and pollutants.The review identifies existing gaps within the current framework and proposes future research avenues to address these challenges.
基金supported by the National Natural Science Foundation of China(22379111 and 22179093)。
文摘Hydrogen peroxide(H_(2)O_(2))electrosynthesis via two-electron oxygen reduction reaction(2e-ORR)is a promising alternative for the energy-intensive anthraquinone process.However,the instability of the catalytic metal sites in the state-of-the-art metal single-atom catalysts(M-SACs)hinders their further industrial applications,and the high potential and valueless oxygen product of the conventional anodic oxygen evolution reaction(OER)further limit the economic efficiency of this technology.To address this,a dynamically local structure reconstruction strategy is proposed to in situ transfer the active sites from unstable metal sites to the stable surrounding carbon sites for efficient and durable 2e^(-)ORR electrocatalysis.For the as-designed Mn-N_(3)O-C catalyst,by reconstructing Mn sites into Mn(^(*)OH),the Mn sites were passivated and carbon sites adjacent to the O atom were verified to be the actual active sites by in situ characterization and theoretical calculation.Consequently,Mn-N_(3)O-C exhibited>80%Faradaic efficiency and superior long-term durability over 100 h for H_(2)O_(2)electrosynthesis at~120 mA cm^(-2).In addition,coupling anodic ethylene glycol oxidation reaction(EGOR)further improves the efficiency and economic viability of the H_(2)O_(2)electrosynthesis system.This two-pronged strategy thus opens up a new opportunity for the development of stable H_(2)O_(2)electrosynthesis with low energy consumption and superior economic performance.
基金supported by the National Natural Science Foundation of China(No.52221004)the Shenzhen Science and Technology Program(No.RCJC20221008092758099)+1 种基金the Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023004)the Guangdong Higher Education Institutions Innovative Research Team of Urban Water Cycle and Ecological Safety(No.2023KCXTD053).
文摘Electrocatalytic CO_(2) reduction(ECR)is a promising approach for achieving carbon neutrality due to its ability to convert CO_(2) to valuable chemicals.Recent advances have significantly enhanced the ECR performance of various catalysts by tuning their oxidation states,particularly for Cu-based catalysts that can reduce CO_(2) to multiple products.However,the oxidation state of copper(OSCu),especially Cu+,changes during the reaction process,posing significant challenges for both catalyst characterization and performance.In this review,the current understanding of the effect of oxidation states on product selectivity was first discussed.A comprehensive overview of in situ/operando characterization techniques,used to monitor the dynamic evolution of oxidation states during ECR,was then provided.Various strategies for stabilizing oxidation states through modification of catalysts and manipulation of external conditions were discussed.This review aimed to deepen the understanding of oxidation states in ECR and enlighten the development of more efficient electrocatalysts.
基金The authors sincerely appreciate funding from“Producing Hydrogen in Trentino-H2@TN”(PAT-Trento)through the research grant(SAP 40104237)Researchers Supporting Project number(RSP2025R399)King Saud University,Riyadh,Saudi Arabia.
文摘Simultaneously inducing dual built-in electric fields(EFs)both within a single component and at the heterojunction interface creates a dual-driving force that is crucial for promoting spatial charge separation.This is particularly significant in challenging coupled systems,such as CO_(2)photoreduction integrated with selective oxidation of toluene to benzaldehyde.However,developing such a system is quite challenging and often requires a precise design and engineering.Herein,we demonstrate a unique Ni-CdS@Ni(OH)_(2)heterojunction synthesized via an in-situ self-assembly method.Comprehensive mechanistic and theoretical investigations reveal that the NiCdS@Ni(OH)_(2)heterojunction induces dual electric fields(EFs):an intrinsic polarized electric-field within the CdS lattice from Ni doping and an interfacial electric-field from the growth of ultrathin nanosheets of Ni(OH)_(2)on NiCdS nanorods,enabling efficient spatial charge separation and enhanced redox potential.As proof of concept,the Ni-CdS@Ni(OH)_(2)heterojunction simultaneously exhibits outstanding bifunctional photocatalytic performance,producing CO at a rate of 427μmol g^(-1)h^(-1)and selectively oxidizing toluene to benzaldehyde at a rate of 1476μmol g^(-1)h^(-1)with a selectivity exceeding 85%.This work offers a promising strategy to optimize the utilization of photogenerated carriers in heterojunction photocatalysts,advancing synergistic photocatalytic redox systems.
文摘Layered transition metal hydroxides show distinct advantages in separately co-catalyzing CO_(2)reduction and H_(2)O oxidation at the electron-accumulating and hole-accumulating sites of wrapped heterojunction photocatalysts,while concurrently preventing side reactions and photocorrosion on the semiconductor surface.Herein,Ni-Co bimetallic hydroxides with varying Ni/Co molar ratios(Ni_(x)Co_(1-x)(OH)_(2),x=1,0.75,0.5,0.25,and 0)were grown in situ on a model 2D/2D S-scheme heterojunction composed of Cu_(2)O nanosheets and Fe_(2)O_(3)nanoplates to form a series of Cu_(2)O/Fe_(2)O_(3)@Ni_(x)Co_(1-x)(OH)_(2)(CF@NiCo)photocatalysts.The combined experimental and theoretical investigation demonstrates that incorporating an appropriate amount of Co into Ni(OH)_(2)not only modulates the energy band structure of Ni_(x)Co_(1-x)(OH)_(2),balances the electron-and hole-trapping abilities of the bifunctional cocatalyst and maximizes the charge separation efficiency of the heterojunction,but also regulates the d-band center of Ni_(x)Co_(1-x)(OH)_(2),reinforcing the adsorption and activation of CO_(2)and H_(2)O on the cocatalyst surface and lowering the rate-limiting barriers in the CO_(2)-to-CO and H_(2)O-to-O_(2)conversion.Benefiting from the Ni-Co synergy,the redox reactions proceed stoichiometrically.The optimized CF@Ni_(0.75)Co_(0.25)achieves CO and O_(2)yields of 552.7 and 313.0μmol gcat^(-1)h^(-1),respectively,11.3/9.9,1.6/1.7,and 4.5/5.9-fold higher than those of CF,CF@Ni,and CF@Co.This study offers valuable insights into the design of bifunctional noble-metal-free cocatalysts for high-performance artificial photosynthesis.
文摘Plastics are ubiquitous in human life and pose certain hazards to the environment and human body.The increasing amount of CO_(2)in the atmosphere will lead to the greenhouse effect.Therefore,it is urgent to treat microplastic waste and CO_(2)by using environmentally friendly and efficient technologies.In this work,we developed an efficient photoelectrocatalytic system composed of Ni single atoms(Ni SAs)supported by P,N-doped amorphous NiFe_(2)O_(4)(Ni SAs/A-P-N-NFO)as anode and Ag nanoparticles(Ag NPs)supported by CuO/Cu_(2)O nanocubes(Ag NPs@CuO/Cu_(2)O NCs)as cathode for microplastic oxidation and CO_(2)reduction.The Ni SAs/A-P-N-NFO was synthesized by calcination-H_(2)reduction method,and it achieved a Faraday efficiency of 93%for the oxidation reaction of poly(ethylene terephthalate)(PET)solution under AM 1.5 G light.As a photocathode,the synthesized Ag NPs@CuO/Cu_(2)O NCs was utilized to reduce CO_(2)to ethylene and CO at 1.5 V vs.RHE with selectivity of 42%and 55%,respectively.This work shows that the photoelectrocatalysis,as an environmentally friendly technology,is a feasible strategy for reducing the environmental and biological hazards of light plastics,as well as for efficient CO_(2)reduction.
基金supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
文摘Electrochemical nitrate reduction(eNO_(3)RR)and nitric oxide reduction(eNORR)to ammonia have emerged as promising and sustainable alternatives to the traditional Haber-Bosch method for ammonia production,particularly within the recently proposed reverse artificial nitrogen cycle route:N_(2)→NO_(x)→NH_(3).Notably,experimental studies have demonstrated that eNORR exhibits superior performance over eNO_(3)RR on Cu6Sn5 catalysts.However,the fundamental mechanisms underlying this difference remain poorly understood.Herein,we performed systematic theoretical calculations to explore the reaction pathways,electronic structure effects,and potential-dependent Faradic efficiency associated with ammonia production via these two distinct electrochemical pathways(eNORR and eNO_(3)RR)on Cu6Sn5.By implementing an advanced‘adaptive electric field controlled constant potential(EFC-CP)’methodology combined with microkinetic modeling,we successfully reproduced the experimental observations and identified the key factors affecting ammonia production in both reaction pathways.It was found that eNORR outperforms eNO_(3)RR because it circumvents the ^(*)NO_(2) dissociation and ^(*)NO_(2) desorption steps,leading to distinct surface coverage of key intermediates between the two pathways.Furthermore,the reaction rates were found to exhibit a pronounced dependence on the surface coverage of ^(*)NO in eNORR and ^(*)NO_(2) in eNO_(3)RR.Specifically,the facile desorption of ^(*)NO_(2) on the Cu6Sn5 surface in eNO_(3)RR limits the attainable surface coverage of ^(*)NO,thereby impeding its performance.In contrast,the eNORR can maintain a high surface coverage of adsorbed ^(*)NO species,contributing to its enhanced ammonia production performance.These fundamental insights provide valuable guidance for the rational design of catalysts and the optimization of reaction routes,facilitating the development of more efficient,sustainable,and scalable techniques for ammonia production.
基金financially supported by the National Natural Science Foundation of China (No.22372057)Yunnan Fundamental Research Projects (No.202301AT070059)+2 种基金the Natural Science Foundation of Hunan Province (No.2023JJ30121)the Natural Science Foundation of Changsha (No.KQ2208259)the Fundamental Research Funds for the Central Universities (No.202044011)。
文摘Perovskite oxides have shown great potential application in fuel cells due to the unique crystal structures and tunable composition as well as effective capability toward the oxygen reduction reaction(ORR),whereas the investigation on the electrocatalytic performance of perovskite oxides toward the two-electron ORR to H_(2)O_(2)production remains very limited.Herein,a facile synthetic method has been developed to prepare La_(2)Sn_(2)O_(7)@La-doped ZnSnO_(3)heterostructures comprising of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).The optimal La_(2)Sn_(2)O_(7)@Ladoped ZnSnO_(3)heterostructures catalyst exhibits a significantly improved two-electron ORR performance to H_(2)O_(2)production with onset potential of 0.77 V and large current density of 2.51 m A.cm^(-2)at 0.1 V compared to ZnSnO_(3)(0.75 V,1.80 m A.cm^(-2),0.11 m A) as well as maintains high H_(2)O_(2)selectivity of 80%,which has been theoretically demonstrated to be contributed to the synergistic effect of amorphous La_(2)Sn_(2)O_(7)and crystalline La-doped ZnSnO_(3).Moreover,high H_(2)O_(2)yield rate of 2.9 m M.h^(-1)at 0.1 V can be achieved with a superior turnover frequency(TOF) of3.31 × 10^(-2)s^(-1)compared to the ZnSnO_(3)catalyst(2.10 × 10^(-2)s^(-1)).This work reveals the great potential of perovskite oxide as promising candidates for the environmentally friendly synthesis of hydrogen peroxide.
基金the Young Elite Scientists Sponsorship Program by CAST(2021QNRC001)Natural Science Foundation of Chongqing(CSTB2022NSCQ-MSX0557,cstb2023nscq-msx0979)+3 种基金Talent Introduction of Chongqing University of Science and Technology(ckrc2021050,ckrc20230401,ckrc2021053)the Science and Technology Research Program of Chongqing Municipal Education Commission(KJQN202201532,KJQN202301542)the National Natural Science Foundation of China(22109016)Open Research Fund of CNMGE Platform&NSCC-TJ(CNMGE2023016).
文摘The development of efficient and durable electrocatalysts for oxygen reduction reaction(ORR)holds a pivotal significance in the successful commercialization of proton exchange membrane fuel cells(PEMFCs)but is still challenging.Herein,we report a worm-liked PtCu nanocrystals dispersed on nitrogen-doped carbon hollow microspheres(Pt_(0.38)Cu_(0.62)/N-HCS).Benefiting from its structural and compositional advantages,the resulting Pt_(0.38)Cu_(0.62)/N-HCS catalyst delivers exceptional electrocatalytic activity for ORR,with a half-wave potential(E_(1/2))of 0.837 V,a mass activity of 0.672 A mgPt^(-1),and a Tafel slope of 50.66 mV dec^(-1),surpassing that of commercial Pt/C.Moreover,the Pt_(0.38)Cu_(0.62)/N-HCS follows the desired four-electron transfer mechanism throughout the ORR process,thereby displaying a high selectivity for direct reduction of O_(2)to H_(2)O.Remarkably,this catalyst also showcases high stability,with only a 25 mV drop in E_(1/2)after 10,000 cycles in an acidic electrolyte.Theoretical calculations elucidate the incorporation of Cu into Pt lattice induces compressive strain,which effectively tailors the d band center of Pt active sites and strengthens the surface chemisorption of O_(2)molecules on PtCu alloys.Consequently,the Pt_(0.38)Cu_(0.62)/N-HCS catalyst exhibits an improved ability to adsorb O_(2)molecules on its surface,accelerating the reaction kinetics of O_(2)conversion to*OOH.Additionally,Cu atoms,not only serving as sacrificial anode,undergo preferential oxidation during PEMFCs operation when compared to Pt,but also the stable Cu species in PtCu alloys contributes significantly to maintaining the strain effect,collectively enhancing both activity and durability.Overall,this research offers an effective and promising approach to enhance the activity and stability of Pt-based ORR electrocatalysts in PEMFCs.
基金supported by the National Key Research and Development Program of China(No.2019YFC0408500)the Scientific Research Project of China State Construction Engineering Corporation Limited(CSCEC-2022-K-(36))the Scientific Research Project of CSCEC AECOM Consultants Corporation Limited(XBSZKY2216).
文摘Anaerobic digestion(AD),as an eco-friendly biological process,shows potential for the decomposition of leachate produced by waste incineration power plants.In this study,the effects of Fe oxides nano-modified pumice(FNP)were investigated on the fresh leachate AD process.Firstly,a simple hydrothermal method was used to prepare FNP,then introduced into the UASB reactor to evaluate its AD efficiency.Results showed that the inclusion of FNP could shorten the lag phase by 10 days compared to the control group.Furthermore,cumulative methane production in the FNP group was enhanced by 20.11%.Mechanistic studies suggested that hydrogenotrophic methanogenesis in the FNP group was more pronounced due to the influence of key enzymes(i.e.,dehydrogenase and coenzyme F420).Microbial community analysis demonstrated that FNP could enhance the abundance of Methanosarcina,Proteobacteria,Sytrophomonas,and Limnobacter,which might elevate enzyme activity involved in methane production.These findings suggest that FNP might mediate interspecies electron transfer among these microorganisms,which is essential for efficient leachate treatment.
基金supported by the Natural Science Foundation of Heilongjiang Province(No.ZD2022E007).
文摘The insufficient electrocatalytic activity and CO_(2)resistance hinder the application of cathode mate-rial for solid oxide fuel cells(SOFCs).In this study,we introduce a series of Pr-doped perovskite Bi_(0.8-x)Pr_(x)Ca_(0.2)FeO_(3-δ)(BPCF_(x),x=0,0.10,0.15,0.20)as candidate cathode materials,with a focus on its phase structure,oxygen desorption ability,catalytic activity,and electrochemical reduction kinetics.Among all the components,the Bi_(0.6)Pr_(0.2)Ca_(0.2)FeO_(3-δ)(BPCF0.20)catalyst shows impressive oxygen reduc-tion reaction(ORR)activity,with a low polarization resistance of 0.06Ωcm^(2)at 700℃and peak power density of 810 mW cm^(−2)at 800℃.Moreover,the BPCF0.20 cathode shows outstanding CO_(2)resistance in different CO_(2)concentrations(1%-10%)due to the larger average bond energy and higher relative acidity of Bi,Pr,and Fe ions.These findings demonstrate that BPCF_(x)are advanced cathode electrocatalysts for SOFCs.
基金supported by the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.SJCX23_0120)the National Natural Science Foundation of China(Nos.22275088 and 52101260)+3 种基金the Project of Shuangchuang Scholar of Jiangsu Province(No.JSSCBS20210212)the Fundamental Research Funds for the Central Universities(No.30921011203)the Start-Up Grant(No.AE89991/340)from Nanjing University of Science and Technology,the Foundation of Jiangsu Educational Committee(No.22KJB310008)the Senior Talent Program of Jiangsu University(No.20JDG073).
文摘The reduction of global carbon emissions and the achievement of carbon neutrality have become the focus of addressing climate change and global warming.Electrochemical CO_(2) reduction(CO_(2)RR),as a technology that can efficiently convert CO_(2) into value-added products,is receiving widespread attention.This article reviews the current research status of Cu/metal oxide heterostructures in the field of electrochemical reduction of CO_(2).The review first introduces the importance of electrochemical reduction of CO_(2) and the application potential of Cu/metal oxide heterostructures in this field.Subsequently,a comprehensive discussion is presented on the exploration of various Cu/metal oxide heterostructures and their corresponding structure-performance relationship,with particular emphasis on the catalysts'activity,selectivity,stability and the nature of active sites.Lastly,the review provides an overview of the current research challenges and future development trends in this field.
基金supported by the National Natural Science Foundation of China(No.22101289)Hundred Talents Programs in Chinese Academy of Science,and the Ningbo S&T Innovation 2025 Major Special Program(No.2022Z205).
文摘Electrochemical CO_(2) reduction reaction(CO_(2)RR),driven by renewable energy,offers a promising solution to mitigate increasing CO_(2) emissions and establish a carbon-neutral cycle.Copper is a highly selective and active catalyst for CO_(2)RR but suffers from structural reconstruction challenges.Hybrid organic/inorganic materials address these issues by offering customizable compositions and interfaces.Recently,Buonsanti’s team developed hybrid Cu@AlOx nanocrystals with tunable alumina shells via a colloidal atomic layer deposition approach,achieving stable and selective methane production during CO_(2)RR.Mechanistic studies reveal that the alumina shell stabilizes oxidized copper species through Cu^(2+)-O-Al motifs coordinated with AlO_(4) Lewis acid sites,reducing copper dissolution and structural reconstruction.This study provides key insights into the mechanism underlying stabilization,highlighting the critical role of Lewis acidity in preserving the structural integrity of the catalyst.This highlight review aims to inspire the development of other high-performance and stable catalysts through colloidal atomic layer deposition strategies.
文摘Mining activities have created great wealth, but they have also discharged large quantities of tailings. As an important source of heavy metal contamination, sulfide tailings are usually disposed of in open-air impoundments and thus are exposed to microbial oxidation. Microbial activities greatly enhance sulfide oxidation and result in the release of heavy metals and the precipitation of iron (oxy) hydroxides and sulfates. These secondary minerals in turn influence the mobility of dissolved metals and play important roles in the natural attenuation of heavy metals. Elucidating the microbe–mineral interactions in tailings will improve our understanding of the environmental consequence of mining activities.
基金supported by the National Natural Science Foundation of China (Nos. 52192684 and 52270136)the National Key Research and Development Project (No. 2020YFC1908704)China Three Gorges Corporation (No. 202003166)。
文摘To improve the sludge conditioning efficiency without increasing the ozone dose,an in-situ sludge reduction process based on Mn^(2+)-catalytic ozonation conditioning was proposed.Using ozone conditioning alone as a control,a lab-scale sequencing batch reactor coupled with ozonated sludge recycle was evaluated for its operating performance at an ozone dose of 75 mg O_(3)/g VSS and 1.5 mmol/L Mn^(2+)addition.The results showed a 39.4%reduction in MLSS and an observed sludge yield of 0.236 kg MLSS/kg COD for the O_(3)+Mn^(2+)group compared to the O_(3)group (15.3%and 0.292 kg MLSS/kg COD),accompanied by better COD,NH_(4)^(+)-N,TN and TP removal,improved effluent SS and limited impact on excess sludge properties.Subsequently,activity tests,BIOLOG ECO microplates and 16S rRNA sequencing were applied to elucidate the changing mechanisms of Mn^(2+)-catalytic ozonation related to microbial action:(1) Dehydrogenase activity reached a higher peak.(2) Microbial utilization of total carbon sources had an elevated effect,up to approximately 18%,and metabolic levels of six carbon sources were also increased,especially for sugars and amino acids most pronounced.(3) The abundance of Defluviicoccus under the phylum Proteobacteria was enhanced to 12.0%and dominated in the sludge,they had strong hydrolytic activity and metabolic capacity.Denitrifying bacteria of the genus Ferruginibacter also showed an abundance of 7.6%,they contributed to the solubilization and reduction of sludge biomass.These results could guide researchers to further reduce ozonation conditioning costs,improve sludge management and provide theoretical support.
基金financially supported by the National Natural Science Foundation of China (No.52200055)the Natural Science Foundation of Jiangsu Province (No.BK20210483)+1 种基金China Postdoctoral Science Foundation (No.2022T150271)the Natural Science Research of Jiangsu Higher Education Institutions of China (No.23KJB610001)。
文摘Water scarcity is an escalating global crisis,posing a severe threat to populations worldwide.Consequently,exploring various materials to remove emerging contaminants from freshwater sources has garnered significant attention.In this regard,single-atom catalysis(SACs) has emerged as a catalyst of scientific progress in water purification and treatment methodologies during recent decades.SACs exhibit exceptional catalytic activity,selectivity and stability,due to their near-perfect atom utilization,highly unsaturated coordination environment and uniform reaction centers.However,a comprehensive and critical review encompassing the successful integration of SACs into water purification processes needs to be completed.This review aims to accentuate recent trends by presenting the synthesis,structure,and environment and energy application-relevant properties of SACs.The results show that a comprehensive and multi-perspective summary of the advantages of SACs in environmental remediation can have significant benefits,such as fast kinetics,costeffectiveness,selectivity.The oxidation and reduction processes of SACs and functional SACs materials in water purification were emphasized.Furthermore,the last section is devoted to the current research gaps and further perspectives on the application of SACs in water treatment,which are summarized and analyzed.
基金We acknowledge the National Natural Science Foundation of China(No.22275134)for fi nancial support.
文摘N-doped carbon materials,with their applications as electrocatalysts for the oxygen reduction reaction(ORR),have been extensively studied.However,a negletcted fact is that the operating potential of the ORR is higher than the theoretical oxida-tion potential of carbon,possibly leading to the oxidation of carbon materials.Consequently,the infl uence of the structural oxidation evolution on ORR performance and the real active sites are not clear.In this study,we discover a two-step oxida-tion process of N-doped carbon during the ORR.The fi rst oxidation process is caused by the applied potential and bubbling oxygen during the ORR,leading to the oxidative dissolution of N and the formation of abundant oxygen-containing functional groups.This oxidation process also converts the reaction path from the four-electron(4e)ORR to the two-electron(2e)ORR.Subsequently,the enhanced 2e ORR generates oxidative H_(2)O_(2),which initiates the second stage of oxidation to some newly formed oxygen-containing functional groups,such as quinones to dicarboxyls,further diversifying the oxygen-containing functional groups and making carboxyl groups as the dominant species.We also reveal the synergistic eff ect of multiple oxygen-containing functional groups by providing additional opportunities to access active sites with optimized adsorption of OOH*,thus leading to high effi ciency and durability in electrocatalytic H_(2)O_(2) production.
文摘Atomically-dispersed metal-based materials represent an emerging class of photocatalysts attributed to their high catalytic activity,abundant surface active sites,and efficient charge separation.Nevertheless,the roles of different forms of atomically-dispersed metals(i.e.,single-atoms and atomic clusters)in photocatalytic reactions remain ambiguous.Herein,we developed an ethylenediamine(EDA)-assisted reduction method to controllably synthesize atomically dispersed Au in the forms of Au single atoms(Au_(SA)),Au clusters(Au_(C)),and a mixed-phase of Au_(SA)and Au_(C)(Au_(SA+C))on CdS.In addition,we elucidate the synergistic effect of Au_(SA)and Au_(C)in enhancing the photocatalytic performance of CdS substrates for simultaneous CO_(2)reduction and aryl alcohol oxidation.Specifically,Au_(SA)can effectively lower the energy barrier for the CO_(2)→*COOH conversion,while Au_(C)can enhance the adsorption of alcohols and reduce the energy barrier for dehydrogenation.As a result,the Au_(SA)and Au_(C)co-loaded CdS show impressive overall photocatalytic CO_(2)conversion performance,achieving remarkable CO and BAD production rates of 4.43 and 4.71 mmol g^(−1)h^(−1),with the selectivities of 93%and 99%,respectively.More importantly,the solar-to-chemical conversion efficiency of Au_(SA+C)/CdS reaches 0.57%,which is over fivefold higher than the typical solar-to-biomass conversion efficiency found in nature(ca.0.1%).This study comprehensively describes the roles of different forms of atomically-dispersed metals and their synergistic effects in photocatalytic reactions,which is anticipated to pave a new avenue in energy and environmental applications.
