With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate...With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate and regeneration of the electrolyte,this technology faces challenges such as difficulty in maintaining long-term stable operation and excessive costs.The pure water CO_(2)electrolyzers are believed to be the ultimate solution to eliminate the salt depreciation and electrolyte issues.This study develops an in-situ method tailored for CO_(2)reduction in pure water.By employing distribution of relaxation times(DRT)analysis and in-situ electrochemical active surface area(ECSA)measurements,we carried out a comprehensive investigation into the mass transport and electrochemical active surface area of gas diffusion electrodes(GDE)under pure water conditions.The maximum 89%CO selectivity and high selectivity(>80%)in the range of 0-300 mA/cm^(2)were achieved using commercial Ag nanoparticles by rational design of catalyst layer.We found that ionomers influence the CO_(2)electrolyzers performance via affecting local pH,GDE-membrane interface,and CO_(2)transport,while catalyst loading mainly influences the active area and CO_(2)transport.This work provides benchmark and insights for future pure water CO_(2)electrolyzers development.展开更多
Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechani...Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.展开更多
Graphene,owing to its exceptional electronic,optical,thermal,and mechanical properties,has emerged as a highly promising material.Currently,the synthesis of large-area graphene films on metal substrates via chemical v...Graphene,owing to its exceptional electronic,optical,thermal,and mechanical properties,has emerged as a highly promising material.Currently,the synthesis of large-area graphene films on metal substrates via chemical vapor deposition remains the predominant approach for producing high-quality graphene.To realize the potential applications of graphene,it is essential to transfer graphene films to target substrates in a manner that is non-destructive,clean,and efficient,as this significantly affects the performance of graphene devices.This review examines the current methods for graphene transfer from three perspectives:non-destructive transfer,clean transfer,and high-efficiency transfer.It analyzes and compares the advancements and limitations of various transfer techniques.Finally,the review identifies the key challenges faced by current graphene transfer methods and anticipates future developmental prospects.展开更多
Through literature analysis and case study, the introduction history, variety selection (high bush, half high bush, low bush) and regional cultivation techniques of blueberry in China were summarized, and the practica...Through literature analysis and case study, the introduction history, variety selection (high bush, half high bush, low bush) and regional cultivation techniques of blueberry in China were summarized, and the practical effects of precision cultivation (water and fertilizer integration, wild planting) and under-forest economic model (forest-blueberry-fungus system, ecological tourism) were evaluated. It provided a technical reference for expanding the planting scale of blueberry and improving the fruit quality.展开更多
The addition of cold flow improvers(CFIs)is considered as the optimum strategy to improve the cold flow properties(CFPs)of diesel fuels,but this strategy is always limited by the required large dosage.To obtain low-do...The addition of cold flow improvers(CFIs)is considered as the optimum strategy to improve the cold flow properties(CFPs)of diesel fuels,but this strategy is always limited by the required large dosage.To obtain low-dosage and high-efficiency CFIs for diesel,1,2,3,6-tetrahydrophthalic anhydride(THPA)was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylatetrans anethole copolymers(C_(14)MC-TA).The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-TA-THPA)were synthesized and compared with the binary copolymers of C_(14)MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-THPA).Results showed that C_(14)MC-THPA achieved the best depressive effects on the cold filter plugging point(CFPP)and solid point(SP)by 11℃and 16℃at a dosage of 1250 mg/L and monomer ratio of 6:1,while 1500mg/L C_(14)MC-TA(1:1)reached the optimal depressive effects on the CFPP and SP by 12℃and 18℃.THPA introduction significantly improved the depressive effects of C_(14)MC-TA.Lower dosages of C_(14)MCTA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C_(14)MC-TA and C_(14)MC-THPA.When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L,the improvement effect of C_(14)MC-TA-THPA on diesel reached the optimum level,and the CFPP and SP were reduced by 13℃and 19℃,respectively.A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios,dosages,and depressive effects of CFIs in diesel.Surface analysis results showed that C_(14)MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L,and the CFPP and SP decreased by 14℃ and 19℃,respectively.The predicted results were consistent with the actual ones.Additionally,the improvement mechanism of these copolymers in diesel was also explored.展开更多
The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical a...The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical and fine chemical synthesis.Here,we report a PdNi single-atom alloy(SAA)catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles(NPs)applied for Suzuki coupling reactions and Heck coupling reactions.The 0.1%PdNi SAA exhibits extraordinary catalytic activity(reaction rate:17,032.25 mmol h^(-1)gPd^(-1))toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃for 1 h.The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms,which provides abundant sites and electrons for the adsorption and fracture of the C-X(X=Cl,Br,I)bond.Moreover,our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.展开更多
The development of atomically dispersed platinum-based catalysts with high performance and welldefined active site structures is crucial for the commercialization of water electrolysis for hydrogen production.Herein,w...The development of atomically dispersed platinum-based catalysts with high performance and welldefined active site structures is crucial for the commercialization of water electrolysis for hydrogen production.Herein,we propose a coordination dual-shell synergistic regulation mechanism of coal pitchderived carbon-supported single atom Pt-N_(x)O_(y)-S_(1)catalytic sites by a self-assembly-pyrolysis strategy for promoting hydrogen evolution reaction(HER).The Pt-N_(3)O1-S_(1)sites exhibited the highest HER performance,with an overpotential of 92 mV at a current density of 400 mA cm^(-2).At 50 mV,the turnover frequency was 34.04 s^(-1)and the mass activity was 22.83 A mg_(Pt)^(-l),which is 63.4 times that of the 20%Pt/C catalyst.Theoretical calculations revealed that the coordination dual-shell impacts the electronic structure of the Pt atoms and the adsorption strength towards reactants synergistically.The S atoms in the second coordination shell weakened the strength of Pt-N first shell,resulting the more surface valence electrons around Pt atoms,exhibiting the most suitable adsorption free energy and enhancing the adsorption of H^(+)on Pt-N_(3)O_(1)-S_(1)sites,thus enhancing the electrocatalytic HER process by promoting Volmer step.This work reveals that coordination dual-shell synergistic regulation is an effective strategy for enhancing the electrocatalytic reaction process.展开更多
Efficient catalysis of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is essential for the rechargeable zinc-air batteries(R-ZABs).However,challenges remain due to the scarcity of effective bifunc...Efficient catalysis of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is essential for the rechargeable zinc-air batteries(R-ZABs).However,challenges remain due to the scarcity of effective bifunctional electrocatalysts and limited understanding of the structure-activity relationships.Pyrrole-type single-atom catalysts(SACs)with unique electronic structures have emerged as promising electrocatalysts.In this work,we combine density functional theory(DFT)calculations and experimental studies to systematically explore the structure-activity relationships and potential of pyrrole-type transition metal-N_(3)(TM-po-N_(3))as bifunctional catalysts.DFT calculations reveal that differences in the dependence of ORR and OER activities on the free energy of adsorption of reaction intermediates significantly affect the TM-po-N_(3)bifunctional activity and identify magnetic Cu-po-N_(3)as the best candidate.The bifunctional activity of Cu-po-N_(3)originates from interactions between spin-polarized out-of-plane Cu_3d and O_2s+2p orbitals.Theoretical predictions are validated experimentally,showing that the synthesized Cu-SAC/NC exhibits excellent bifunctional performance with a small potential gap of 0.666 V.Additionally,the assembled R-ZABs display a high-power density of 170 mW cm^(-2)and long-term stability,with the charge-discharge voltage gap increasing by only 0.01 V over 240 h.This work provides new insights into the design of efficient bifunctional catalysts.展开更多
Hydrogen evolution reaction(HER)and oxygen evolution/reduction reaction(OER/ORR)relying on high-performance and low-cost single-atom catalysts(SACs)driven by renewable energy sources offer a sustainable route to carbo...Hydrogen evolution reaction(HER)and oxygen evolution/reduction reaction(OER/ORR)relying on high-performance and low-cost single-atom catalysts(SACs)driven by renewable energy sources offer a sustainable route to carbon-neutral chemicals and fuels.Herein,first-principles calculations were performed to investigate the catalytic HER/OER/ORR activity of a novel graphitic carbon nitride monolayer(g-C_(7)N_(3))supported single transition metal(TM@g-C_(7)N_(3)).High stability as well as positively charged active site(TM-site)and desirable electrical conductivity lay the foundation for TM@g-C_(7)N_(3)acting as efficient HER/OER/ORR electrocatalysts.We screened out the non-noble-metal Rh@g-C_(7)N_(3)SAC exhibiting great potential as the trifunctional electrocatalysts for water splitting(η^(HER)=0.06 V andηOER=0.46 V)and a metal-air battery(η^(ORR)=0.28 V)on both kinetic and thermodynamic scales,whereas the Ni@g-C_(7)N_(3)can be served as a bifunctional OER/ORR catalyst with a low overpotential of 0.33 V/0.31 V,for both of which the high thermodynamic stability and oxidation barrier guarantee their outstanding performances at ambient conditions.The mechanism analysis indicates the filling of d-orbital electrons of TM-atom can play an important role in determining the value of an energy descriptor(ΔGOH*),and the suitableΔGOH*values make for the TM@g-C_(7)N_(3)candidates to possess favorable OER/ORR overpotential.Particularly,the Rh-d orbital of Rh@g-C_(7)N_(3)is evidently hybridized with the OH*-p orbital,resulting in the lone electrons initially distributed in the antibonding orbital pairing up and occupying the downward bonding orbital,ensuring OH*can be adsorbed on Rh@g-C_(7)N_(3)appropriately.Moreover,multiple-level descriptors including d-band center,COHP,Nd,andφare used to reveal the origin of the electrocatalytic activity.展开更多
Gamma titanium-aluminum intermetallic compounds(γ-TiAl)have gained considerable attentions in the aerospace industry due to their exceptional thermal resilience and comprehensive attributes,making them a prime exampl...Gamma titanium-aluminum intermetallic compounds(γ-TiAl)have gained considerable attentions in the aerospace industry due to their exceptional thermal resilience and comprehensive attributes,making them a prime example of lightweight and advanced materials.To address the frequent occurrence of burns and severe tool deterioration during the process of high-efficiency deep grinding(HEDG)onγ-TiAl alloys,ultrasonic vibration-assisted high-efficiency deep grinding(UVHEDG)has been emerged.Results indicate that in UVHEDG,the grinding temperature is on average 15.4%lower than HEDG due to the employment of ultrasonic vibrations,enhancing coolant penetration into the grinding area and thus reducing heat generation.Besides,UVHEDG possesses superior performance in terms of grinding forces compared to HEDG.As the material removal volume(MRV)increases,the tangential grinding force(F_(t))and normal grinding force(F_(n))of UVHEDG increase but to a lesser extent than in HEDG,with an average reduction of16.25%and 14.7%,respectively.UVHEDG primarily experiences microfracture of grains,whereas HEDG undergoes large-scale wear later in the process due to increased grinding forces.The surface roughness(R_(a))characteristics of UVHEDG are superior,with the average value of R_(a)decreasing by 46.5%compared to HEDG as MRV increases.The surface morphology in UVHEDG exhibits enhanced smoothness and a shallower layer of plastic deformation.Grinding chips generated by UVHEDG show a more shear-like shape,with the applied influence of ultrasonic vibration on chip morphology,thereby impacting material removal behaviors.These aforementioned findings contribute to enhanced machining efficiency and product quality ofγ-TiAl alloys after employing ultrasonic vibrations into HEDG.展开更多
To solve the problem of only surface carbonation and realize high-efficiency carbonation of recycled coarse aggregate,the method of carbonated recycled coarse aggregate with nano materials pre-soaking was first put fo...To solve the problem of only surface carbonation and realize high-efficiency carbonation of recycled coarse aggregate,the method of carbonated recycled coarse aggregate with nano materials pre-soaking was first put forward.The carbonation effect of modified recycled coarse aggregate with three different carbonation methods was evaluated,and water absorption,apparent density and crush index of modified recycled coarse aggregate were measured.Combined with XRD,SEM,and MIP microscopic analysis,the high-efficiency carbonation strengthening mechanism of modified recycled coarse aggregate was revealed.The experimental results show that,compared with the non-carbonated recycled coarse aggregate,the physical and microscopic properties of carbonated recycled coarse aggregate are improved.The method of carbonation with nano-SiO_(2) pre-soaking can realize the high-efficiency carbonation of recycled coarse aggregate,for modified recycled coarse aggregate with the method,water absorption is reduced by 23.03%,porosity is reduced by 44.06%,and the average pore diameter is 21.82 nm.The high-efficiency carbonation strengthening mechanism show that the pre-socked nano-SiO_(2) is bound to the hydration product Ca(OH)_(2) of the old mortar with nano-scale C-S-H,which can improve the CO_(2) absorption rate,accelerate the carbonation reaction,generate more stable CaCO_(3) and nano-scale silica gel,and bond to the dense three-dimensional network structure to realize the bidirectional enhancement of nano-materials and pressurized carbonation.It is concluded that the method of carbonation with nano-SiO_(2) pre-soaking is a novel high-efficiency carbonation modification of recycled coarse aggregate.展开更多
Reasonably designing highly active,environmentally friendly,and cost-effective catalysts for efficient elimination of pollutants from water is desirable but challenging.Herein,an efficient heterogeneous photo-Fenton c...Reasonably designing highly active,environmentally friendly,and cost-effective catalysts for efficient elimination of pollutants from water is desirable but challenging.Herein,an efficient heterogeneous photo-Fenton catalyst tourmaline(TM)/tungsten oxide(WO_(3-x))(named TW10)containing tungsten/boron/iron(W/B/Fe)synergistic active centers and 90%of cheap natural tourmaline(TM)mineral rich in Fe and B elements.The TW10 catalyst can quickly activate peroxymonosulfate(PMS)to generate massive active free radicals,which may induce the rapid and efficient degradation of tetracycline(TC).The TW10/PMS/Visible light system can effectively degrade up to 98.7%of tetracycline(TC)in actual waters(i.e.seawater,Yellow River,and Yangtze River water),and the catalytic degradation rates reach 1.65,5.569,and 2.38 times higher than those of TM,WO_(3-x),and commercial P25(Degussa,Germany),respectively.In addition,the catalyst can be recycled and reused multiple times.Electron spin resonance spectroscopy(EPR),X-ray photoelectron spectroscopy(XPS),and liquid chromatograph-mass spectrometer(LC-MS)analyses confirm that the synergistic catalytic effect of W/B/Fe sites on the TW10 catalyst accelerates the electron transfer between Fe(Ⅱ)and Fe(Ⅲ),as well as between W(Ⅴ)and W(Ⅵ),and thus promotes the rapid degradation of TC.The catalytic reaction mechanism and degradation pathway of TC were explored.This work provides a feasible route for the design and development of new eco-friendly and efficient catalyst.展开更多
Metal halide perovskite solar cells(PSCs)are one of the most promising photovoltaic devices.Over time,many strategies have been adopted to improve PSC efficiency,and the certified efficiency has reached 26.1%.However,...Metal halide perovskite solar cells(PSCs)are one of the most promising photovoltaic devices.Over time,many strategies have been adopted to improve PSC efficiency,and the certified efficiency has reached 26.1%.However,only a few research groups have fabricated PSCs with an efficiency of>25%,indicating that achieving this efficiency remains uncommon.To develop the PSC industry,outstanding talent must be reserved with the latest technologies.Herein,we summarize the recent developments in high-efficiency PSCs(>25%)and highlight their effective strategies in crystal regulation,interface passivation,and component layer structural design.Finally,we propose perspectives based on current research to further enhance the efficiency and promote the commercialization process of PSCs.展开更多
The isolation of circulating tumor cells(CTCs)from complex biological samples is of paramount signifi-cance for advancing cancer diagnosis,prognosis,and treatment.However,the low concentration of CTCs and nonspecific ...The isolation of circulating tumor cells(CTCs)from complex biological samples is of paramount signifi-cance for advancing cancer diagnosis,prognosis,and treatment.However,the low concentration of CTCs and nonspecific adhesion of white blood cells(WBCs)present challenges that hinder the efficiency and purity of captured CTCs.Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules,enabling effective CTCs separation.Moreover,by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs,the purity of isolated CTCs can be further enhanced.This review offers an in-depth explo-ration of recent advancements,challenges,and opportunities associated with microfluidic-based CTCs iso-lation from biological samples.Firstly,we will comprehensively introduce the microfluidic-based strate-gies for achieving high-efficiency CTCs isolation,which includes the morphological design of microchan-nels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation.Subsequently,a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented,focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification.Finally,we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.展开更多
Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic re...Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition(ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core–shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.展开更多
Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffering from aggregat...Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffering from aggregation and neutralization of internal piezoelectric field caused by polydomains.Here we report a single crystal ZnO of large size and few bulk defects crafted by a hydrothermal method for piezocatalytic hydrogen generation from pure water.It is noteworthy that single-side surface areas of both original as-prepared ZnO and Ga-doped ZnO bulk crystals are larger than 30 cm^(2).The high quality of ZnO and Ga-doped ZnO bulks are further uncovered by high-resolution transmission electron microscope(HRTEM),photoluminescence(PL)and X-ray diffraction(XRD).Remarkably,an outstanding hydrogen production rate of co-catalyst-free Ga-doped ZnO bulk crystal(i.e.,a maximum rate of 5915μmol h^(-1) m^(-2))is observed in pure water triggered by ultrasound in dark,which is over 100 times higher than that of its powder counterpart(i.e.,52.54μmol h^(-1) m^(-2)).The piezocatalytic performance of ZnO bulk crystal is systematically studied in terms of varied exposed crystal facet,thickness and conductivity.Different piezocatalytic performances are attributed to magnitude and distribution of piezoelectric potential,revealed by the finite element method(FEM)simulation.The density functional theory(DFT)calculations are employed to investigate the piezocatalytic hydrogen evolution process,indicating a strong H_(2)O adsorption and a low energy barrier for both H_(2)O dissociation and H2 generation on the stressed Znterminated(0001)ZnO surface.展开更多
The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting sys...The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.展开更多
Transition metal Ni anchored in carbon material represents outstanding 2e^(-) oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity re...Transition metal Ni anchored in carbon material represents outstanding 2e^(-) oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity remains a major challenge.Herein,the NiX/Ni@NCHS composite catalyst with heteroatom doping(O,S)is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal Ni.With the synergistic effect of honeycomb structure and O atom,NiO/Ni@NCHS-700 exhibits an exceptional H_(2)O_(2)selectivity of above 89.1%across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte,and an unexpected H_(2)O_(2)production rate up to 1.47 mol gcat^(-1) h^(-1)@0.2 V,which outperforms most of the state-of-the-art catalyst.Meanwhile,NiS/Ni@NCHS exhibits excellent electrocatalytic performance,with 2e^(-) ORR selectivity of 91.3%,H_(2)O_(2)yield of 1.85@0.3 V.Density functional theory simulations and experiments results reveal that the heteroatom doping(O,S)method has been employed to regulate the adsorption strength of Ni atoms with*OOH,and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active site.The heteroatom doping method in this work provides significant guidance for promoting 2e^(-) ORR electrocatalysis to produce H_(2)O_(2).展开更多
Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by ...Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.展开更多
The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to repl...The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to replace noble metal electrocatalysts.Hence,in this study,we investigate a novel and low-cost bifunctional electrocatalyst consisting of ZnCoMnO_(4) anchored on nitrogen-doped graphene oxide(ZnCoMnO_(4)/N-rGO).Benefiting from the strong Co-N interaction in ZnCoMnO_(4) and the coupled conductive N-rGO,the catalysts exhibit high electrocatalytic activity.Moreover,density functional theory calculations support the dominant role of the strong Co-N electronic interaction,which leads to ZnCoMnO_(4)/N-rGO having more favorable binding energies with O2 and H_(2) O,resulting in fast reaction kinetics.The obtained ZnCoMnO_(4)/N-rGO electrocatalyst exhibits superb bifunctional activity,with a half-wave potential of 0.83 V for the oxygen reduction reaction and a low onset potential of 1.57 V for the oxygen evolution reaction in 0.1 M KOH solution.Furthermore,a Zn-air battery driven by the ZnCoMnO_(4)/N-rGO catalyst shows remarkable discharge/charge performance,with a power density of 138.52 mW cm^(-2) and longterm cycling stability for 48 h.This work provides a promising multifunctional electrocatalyst based on non-noble metals for the storage and conversion of renewable energy.展开更多
基金supported by the National Natural Science Foundation of China(No.52394204)by the Shanghai Municipal Science and Technology Major Project。
文摘With the development of renewable energy,electrochemical carbon dioxide reduction reaction(CO_(2)RR)has become a potential solution for achieving carbon neutrality.However,until now,due to issues with salt precipitate and regeneration of the electrolyte,this technology faces challenges such as difficulty in maintaining long-term stable operation and excessive costs.The pure water CO_(2)electrolyzers are believed to be the ultimate solution to eliminate the salt depreciation and electrolyte issues.This study develops an in-situ method tailored for CO_(2)reduction in pure water.By employing distribution of relaxation times(DRT)analysis and in-situ electrochemical active surface area(ECSA)measurements,we carried out a comprehensive investigation into the mass transport and electrochemical active surface area of gas diffusion electrodes(GDE)under pure water conditions.The maximum 89%CO selectivity and high selectivity(>80%)in the range of 0-300 mA/cm^(2)were achieved using commercial Ag nanoparticles by rational design of catalyst layer.We found that ionomers influence the CO_(2)electrolyzers performance via affecting local pH,GDE-membrane interface,and CO_(2)transport,while catalyst loading mainly influences the active area and CO_(2)transport.This work provides benchmark and insights for future pure water CO_(2)electrolyzers development.
基金Supported by the Interdisciplinary Team Project of Shenyang University of Technology in 2021:Green and Low-carbon(Technology and Evaluation)of Typical Industries of Carbon Peak(2021-70-06)"Double First-class"Construction Project of Liaoning Province in 2020(Scientific Research)(FWDFGD2020041).
文摘Based on the basic principle and mechanism of flue gas denitrification,the commonly used catalysts for flue gas denitrification were introduced firstly,and then the catalytic performance,stability and reaction mechanism of catalysts in the market were analyzed.Different types of catalysts were studied to look for green catalysts with high activity,sulfur resistance,water vapor resistance and other advantages.The mechanism of denitration reaction of green catalysts was discussed,and the laws of formation,propagation and consumption of active species in the reaction process were revealed to provide theoretical basis for optimizing catalyst design and improving reaction conditions.Then the research status and problems of new catalysts for flue gas denitrification were described.Finally,the future development direction of green catalysts for flue gas denitration was discussed to improve the performance and stability of catalysts and meet the performance requirements of denitration catalysts in different industries.
基金supported by the National Key R&D Program of China(2020YFB2009002).
文摘Graphene,owing to its exceptional electronic,optical,thermal,and mechanical properties,has emerged as a highly promising material.Currently,the synthesis of large-area graphene films on metal substrates via chemical vapor deposition remains the predominant approach for producing high-quality graphene.To realize the potential applications of graphene,it is essential to transfer graphene films to target substrates in a manner that is non-destructive,clean,and efficient,as this significantly affects the performance of graphene devices.This review examines the current methods for graphene transfer from three perspectives:non-destructive transfer,clean transfer,and high-efficiency transfer.It analyzes and compares the advancements and limitations of various transfer techniques.Finally,the review identifies the key challenges faced by current graphene transfer methods and anticipates future developmental prospects.
文摘Through literature analysis and case study, the introduction history, variety selection (high bush, half high bush, low bush) and regional cultivation techniques of blueberry in China were summarized, and the practical effects of precision cultivation (water and fertilizer integration, wild planting) and under-forest economic model (forest-blueberry-fungus system, ecological tourism) were evaluated. It provided a technical reference for expanding the planting scale of blueberry and improving the fruit quality.
基金supported from the Natural Science Foundation Project of Shanghai(Nos.23ZR1425300 and 22ZR1426100)Experimental Technical Team Construction Project of Shanghai Education Commission(No.10110N230080)+1 种基金National Natural Science Foundation of China(No.22075183)Research and Innovation Project of Shanghai Municipal Education Commission(No.2023ZKZD54).
文摘The addition of cold flow improvers(CFIs)is considered as the optimum strategy to improve the cold flow properties(CFPs)of diesel fuels,but this strategy is always limited by the required large dosage.To obtain low-dosage and high-efficiency CFIs for diesel,1,2,3,6-tetrahydrophthalic anhydride(THPA)was introduced as a third and polar monomer to enhance the depressive effects of alkyl methacrylatetrans anethole copolymers(C_(14)MC-TA).The terpolymers of alkyl methacrylate-trans anethole-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-TA-THPA)were synthesized and compared with the binary copolymers of C_(14)MC-TA and alkyl methacrylate-1,2,3,6-tetrahydrophthalic anhydride(C_(14)MC-THPA).Results showed that C_(14)MC-THPA achieved the best depressive effects on the cold filter plugging point(CFPP)and solid point(SP)by 11℃and 16℃at a dosage of 1250 mg/L and monomer ratio of 6:1,while 1500mg/L C_(14)MC-TA(1:1)reached the optimal depressive effects on the CFPP and SP by 12℃and 18℃.THPA introduction significantly improved the depressive effects of C_(14)MC-TA.Lower dosages of C_(14)MCTA-THPA in diesel exerted better improvement effects on the CFPP and SP than that of C_(14)MC-TA and C_(14)MC-THPA.When the monomer ratio and dosage were 6:0.6:0.4 and 1000 mg/L,the improvement effect of C_(14)MC-TA-THPA on diesel reached the optimum level,and the CFPP and SP were reduced by 13℃and 19℃,respectively.A 3D nonlinear surface diagram fitted by a mathematical model was also used for the first time to better understand the relationships of monomer ratios,dosages,and depressive effects of CFIs in diesel.Surface analysis results showed that C_(14)MC-TA-THPA achieved the optimum depressive effects at a monomer ratio of 6:0.66:0.34 and dosage of 1000 mg/L,and the CFPP and SP decreased by 14℃ and 19℃,respectively.The predicted results were consistent with the actual ones.Additionally,the improvement mechanism of these copolymers in diesel was also explored.
基金supported by the financial aid from National Science and Technology Major Project of China(No.2021YFB3500700)National Natural Science Foundation of China(Nos.22020102003,22025506 and 22271274)Program of Science and Technology Development Plan of Jilin Province of China(Nos.20230101035JC and 20230101022JC)。
文摘The preparation of Pd-based catalysts with rich electrons and a high atom dispersion rate is of great significance for improving the reactivity of cross-coupling reactions,which is a powerful tool for pharmaceutical and fine chemical synthesis.Here,we report a PdNi single-atom alloy(SAA)catalyst in which isolated Pd single atoms are anchored onto the surface of Ni nanoparticles(NPs)applied for Suzuki coupling reactions and Heck coupling reactions.The 0.1%PdNi SAA exhibits extraordinary catalytic activity(reaction rate:17,032.25 mmol h^(-1)gPd^(-1))toward the Suzuki cross-coupling reaction between 4-bromoanisole and phenylboronic acid at 80℃for 1 h.The excellent activity is supposed to attribute to the 100 percent utilization rate of Pd atoms and the highly stable surface zero-valance Pd atoms,which provides abundant sites and electrons for the adsorption and fracture of the C-X(X=Cl,Br,I)bond.Moreover,our work demonstrates the excellent application prospect of SAAs for cross-coupling reactions.
基金supported by the National Natural Science Foundation of China(22108306,22478432 and 22406191)Taishan Scholars Program of Shandong Province(tsqn201909065)the Natural Science Foundation of Shandong Province(ZR2024JQ004,ZR2021YQ15)。
文摘The development of atomically dispersed platinum-based catalysts with high performance and welldefined active site structures is crucial for the commercialization of water electrolysis for hydrogen production.Herein,we propose a coordination dual-shell synergistic regulation mechanism of coal pitchderived carbon-supported single atom Pt-N_(x)O_(y)-S_(1)catalytic sites by a self-assembly-pyrolysis strategy for promoting hydrogen evolution reaction(HER).The Pt-N_(3)O1-S_(1)sites exhibited the highest HER performance,with an overpotential of 92 mV at a current density of 400 mA cm^(-2).At 50 mV,the turnover frequency was 34.04 s^(-1)and the mass activity was 22.83 A mg_(Pt)^(-l),which is 63.4 times that of the 20%Pt/C catalyst.Theoretical calculations revealed that the coordination dual-shell impacts the electronic structure of the Pt atoms and the adsorption strength towards reactants synergistically.The S atoms in the second coordination shell weakened the strength of Pt-N first shell,resulting the more surface valence electrons around Pt atoms,exhibiting the most suitable adsorption free energy and enhancing the adsorption of H^(+)on Pt-N_(3)O_(1)-S_(1)sites,thus enhancing the electrocatalytic HER process by promoting Volmer step.This work reveals that coordination dual-shell synergistic regulation is an effective strategy for enhancing the electrocatalytic reaction process.
基金supported by the Hainan Province Science and Technology Special Fund(ZDYF2020037)the National Natural Science Foundation of China(22109035,52164028,52274297,22462006)+3 种基金the Postdoctoral Science Foundation of Hainan Province(RZ2100007123)the Basic and Applied Basic Research Foundation of Guangdong Province(2019A1515110558)the Start-up Research Foundation of Hainan University(KYQD(ZR)-20008,20083,20084,21125)Hainan University(XTCX2022HYC05)。
文摘Efficient catalysis of the oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)is essential for the rechargeable zinc-air batteries(R-ZABs).However,challenges remain due to the scarcity of effective bifunctional electrocatalysts and limited understanding of the structure-activity relationships.Pyrrole-type single-atom catalysts(SACs)with unique electronic structures have emerged as promising electrocatalysts.In this work,we combine density functional theory(DFT)calculations and experimental studies to systematically explore the structure-activity relationships and potential of pyrrole-type transition metal-N_(3)(TM-po-N_(3))as bifunctional catalysts.DFT calculations reveal that differences in the dependence of ORR and OER activities on the free energy of adsorption of reaction intermediates significantly affect the TM-po-N_(3)bifunctional activity and identify magnetic Cu-po-N_(3)as the best candidate.The bifunctional activity of Cu-po-N_(3)originates from interactions between spin-polarized out-of-plane Cu_3d and O_2s+2p orbitals.Theoretical predictions are validated experimentally,showing that the synthesized Cu-SAC/NC exhibits excellent bifunctional performance with a small potential gap of 0.666 V.Additionally,the assembled R-ZABs display a high-power density of 170 mW cm^(-2)and long-term stability,with the charge-discharge voltage gap increasing by only 0.01 V over 240 h.This work provides new insights into the design of efficient bifunctional catalysts.
基金supported by the National Natural Science Foundation of China(No.21905175).
文摘Hydrogen evolution reaction(HER)and oxygen evolution/reduction reaction(OER/ORR)relying on high-performance and low-cost single-atom catalysts(SACs)driven by renewable energy sources offer a sustainable route to carbon-neutral chemicals and fuels.Herein,first-principles calculations were performed to investigate the catalytic HER/OER/ORR activity of a novel graphitic carbon nitride monolayer(g-C_(7)N_(3))supported single transition metal(TM@g-C_(7)N_(3)).High stability as well as positively charged active site(TM-site)and desirable electrical conductivity lay the foundation for TM@g-C_(7)N_(3)acting as efficient HER/OER/ORR electrocatalysts.We screened out the non-noble-metal Rh@g-C_(7)N_(3)SAC exhibiting great potential as the trifunctional electrocatalysts for water splitting(η^(HER)=0.06 V andηOER=0.46 V)and a metal-air battery(η^(ORR)=0.28 V)on both kinetic and thermodynamic scales,whereas the Ni@g-C_(7)N_(3)can be served as a bifunctional OER/ORR catalyst with a low overpotential of 0.33 V/0.31 V,for both of which the high thermodynamic stability and oxidation barrier guarantee their outstanding performances at ambient conditions.The mechanism analysis indicates the filling of d-orbital electrons of TM-atom can play an important role in determining the value of an energy descriptor(ΔGOH*),and the suitableΔGOH*values make for the TM@g-C_(7)N_(3)candidates to possess favorable OER/ORR overpotential.Particularly,the Rh-d orbital of Rh@g-C_(7)N_(3)is evidently hybridized with the OH*-p orbital,resulting in the lone electrons initially distributed in the antibonding orbital pairing up and occupying the downward bonding orbital,ensuring OH*can be adsorbed on Rh@g-C_(7)N_(3)appropriately.Moreover,multiple-level descriptors including d-band center,COHP,Nd,andφare used to reveal the origin of the electrocatalytic activity.
基金financially supported by the National Natural Science Foundation of China(Nos.92160301,92060203,52175415 and 52205475)the Science Center for Gas Turbine Project(Nos.P2022-AB-Ⅳ-002-001 and P2023-B-Ⅳ-003-001)+4 种基金the Natural Science Foundation of Jiangsu Province(No.BK20210295)the Superior Postdoctoral Project of Jiangsu Province(No.2022ZB215)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_0355)the Interdisciplinary Innovation Fund for Doctoral Students of Nanjing University of Aeronautics and Astronautics(KXKCXJJ202305)the Fundamental Research Funds for the Central Universities(Nos.NS2023028 and NG2024015)。
文摘Gamma titanium-aluminum intermetallic compounds(γ-TiAl)have gained considerable attentions in the aerospace industry due to their exceptional thermal resilience and comprehensive attributes,making them a prime example of lightweight and advanced materials.To address the frequent occurrence of burns and severe tool deterioration during the process of high-efficiency deep grinding(HEDG)onγ-TiAl alloys,ultrasonic vibration-assisted high-efficiency deep grinding(UVHEDG)has been emerged.Results indicate that in UVHEDG,the grinding temperature is on average 15.4%lower than HEDG due to the employment of ultrasonic vibrations,enhancing coolant penetration into the grinding area and thus reducing heat generation.Besides,UVHEDG possesses superior performance in terms of grinding forces compared to HEDG.As the material removal volume(MRV)increases,the tangential grinding force(F_(t))and normal grinding force(F_(n))of UVHEDG increase but to a lesser extent than in HEDG,with an average reduction of16.25%and 14.7%,respectively.UVHEDG primarily experiences microfracture of grains,whereas HEDG undergoes large-scale wear later in the process due to increased grinding forces.The surface roughness(R_(a))characteristics of UVHEDG are superior,with the average value of R_(a)decreasing by 46.5%compared to HEDG as MRV increases.The surface morphology in UVHEDG exhibits enhanced smoothness and a shallower layer of plastic deformation.Grinding chips generated by UVHEDG show a more shear-like shape,with the applied influence of ultrasonic vibration on chip morphology,thereby impacting material removal behaviors.These aforementioned findings contribute to enhanced machining efficiency and product quality ofγ-TiAl alloys after employing ultrasonic vibrations into HEDG.
基金Funded by Joint Funds of the National Natural Science Foundation of China(No.U1904188)the Jiangxi Provincial Department of Education Science and Technology Project(Nos.GJJ171079,GJJ181023,and GJJ181022)。
文摘To solve the problem of only surface carbonation and realize high-efficiency carbonation of recycled coarse aggregate,the method of carbonated recycled coarse aggregate with nano materials pre-soaking was first put forward.The carbonation effect of modified recycled coarse aggregate with three different carbonation methods was evaluated,and water absorption,apparent density and crush index of modified recycled coarse aggregate were measured.Combined with XRD,SEM,and MIP microscopic analysis,the high-efficiency carbonation strengthening mechanism of modified recycled coarse aggregate was revealed.The experimental results show that,compared with the non-carbonated recycled coarse aggregate,the physical and microscopic properties of carbonated recycled coarse aggregate are improved.The method of carbonation with nano-SiO_(2) pre-soaking can realize the high-efficiency carbonation of recycled coarse aggregate,for modified recycled coarse aggregate with the method,water absorption is reduced by 23.03%,porosity is reduced by 44.06%,and the average pore diameter is 21.82 nm.The high-efficiency carbonation strengthening mechanism show that the pre-socked nano-SiO_(2) is bound to the hydration product Ca(OH)_(2) of the old mortar with nano-scale C-S-H,which can improve the CO_(2) absorption rate,accelerate the carbonation reaction,generate more stable CaCO_(3) and nano-scale silica gel,and bond to the dense three-dimensional network structure to realize the bidirectional enhancement of nano-materials and pressurized carbonation.It is concluded that the method of carbonation with nano-SiO_(2) pre-soaking is a novel high-efficiency carbonation modification of recycled coarse aggregate.
基金supported by the National Natural Science Foundation of China(No.22068027)the“Grassland Talents”Project of Inner Mongolia Autonomous Region(No.CCYCLJ202)the Inner Mongolia University Research Start-up Research Project(No.21300-5205122)。
文摘Reasonably designing highly active,environmentally friendly,and cost-effective catalysts for efficient elimination of pollutants from water is desirable but challenging.Herein,an efficient heterogeneous photo-Fenton catalyst tourmaline(TM)/tungsten oxide(WO_(3-x))(named TW10)containing tungsten/boron/iron(W/B/Fe)synergistic active centers and 90%of cheap natural tourmaline(TM)mineral rich in Fe and B elements.The TW10 catalyst can quickly activate peroxymonosulfate(PMS)to generate massive active free radicals,which may induce the rapid and efficient degradation of tetracycline(TC).The TW10/PMS/Visible light system can effectively degrade up to 98.7%of tetracycline(TC)in actual waters(i.e.seawater,Yellow River,and Yangtze River water),and the catalytic degradation rates reach 1.65,5.569,and 2.38 times higher than those of TM,WO_(3-x),and commercial P25(Degussa,Germany),respectively.In addition,the catalyst can be recycled and reused multiple times.Electron spin resonance spectroscopy(EPR),X-ray photoelectron spectroscopy(XPS),and liquid chromatograph-mass spectrometer(LC-MS)analyses confirm that the synergistic catalytic effect of W/B/Fe sites on the TW10 catalyst accelerates the electron transfer between Fe(Ⅱ)and Fe(Ⅲ),as well as between W(Ⅴ)and W(Ⅵ),and thus promotes the rapid degradation of TC.The catalytic reaction mechanism and degradation pathway of TC were explored.This work provides a feasible route for the design and development of new eco-friendly and efficient catalyst.
基金support from the National Natural Science Foundation of China(Grant Nos.52025028,52332008,52372214,and U22A20137)the Priority Academic Program Development(PAPD)of Jiangsu Higher Education Institutions.
文摘Metal halide perovskite solar cells(PSCs)are one of the most promising photovoltaic devices.Over time,many strategies have been adopted to improve PSC efficiency,and the certified efficiency has reached 26.1%.However,only a few research groups have fabricated PSCs with an efficiency of>25%,indicating that achieving this efficiency remains uncommon.To develop the PSC industry,outstanding talent must be reserved with the latest technologies.Herein,we summarize the recent developments in high-efficiency PSCs(>25%)and highlight their effective strategies in crystal regulation,interface passivation,and component layer structural design.Finally,we propose perspectives based on current research to further enhance the efficiency and promote the commercialization process of PSCs.
基金supported by the National Natural Science Foundation of China(Nos.52025132,22005255,21975209,21621091,22021001,T2241022)the National Science Foundation of Fujian Province of China(No.2022J02059)+2 种基金the Fundamental Research Funds for the Central Universities of China(No.20720220085)the 111 Project(Nos.B17027,B16029)the Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(No.RD2022070601),the New Cornerstone Science Foundation through the XPLORER PRIZE.
文摘The isolation of circulating tumor cells(CTCs)from complex biological samples is of paramount signifi-cance for advancing cancer diagnosis,prognosis,and treatment.However,the low concentration of CTCs and nonspecific adhesion of white blood cells(WBCs)present challenges that hinder the efficiency and purity of captured CTCs.Microfluidic-based strategies utilize precise fluid control at the micron level to incorporate specific micro/nanostructures or recognition molecules,enabling effective CTCs separation.Moreover,by employing surface modification designs that exhibit exceptional anti-adhesion properties against WBCs,the purity of isolated CTCs can be further enhanced.This review offers an in-depth explo-ration of recent advancements,challenges,and opportunities associated with microfluidic-based CTCs iso-lation from biological samples.Firstly,we will comprehensively introduce the microfluidic-based strate-gies for achieving high-efficiency CTCs isolation,which includes the morphological design of microchan-nels for physical force-based CTCs isolation and the specific modification of microchannel surfaces for affinity-based CTCs isolation.Subsequently,a review of recent research advances in microfluidic-based high-purity CTCs isolation is presented,focusing on strategies that decrease the nonspecific adhesion of WBCs through surface micro-/nanostructure construction or chemical and biological modification.Finally,we will summarize the article by providing the prospective opportunities and challenges for the future development of microfluidic-based CTCs isolation.
基金supported by the National Natural Science Foundation of China(21872160,21802094,21673269)the National Science Fund for Distinguished Young Scholars(21825204)+1 种基金the National Key R&D Program of China(2017YFA0700101)the Natural Science Basic Research Plan in Shaanxi Province of China(2018JQ2038)~~
文摘Electrocatalysis is a promising approach to clean energy conversion due to its high efficiency and low environmental pollution. Noble metal materials have been studied to show high activity toward electrocatalyltic reactions, although such applications remain restricted by the high cost and poor durability of the noble metals. By precisely adjusting the catalyst composition, size, and structure, electrocatalysts with excellent performance can be obtained. Atomic layer deposition(ALD) is a technique used to produce ultrathin films and ultrafine nanoparticles at the atomic level. It possesses unique advantages for the controllable design and synthesis of electrocatalysts. Furthermore, the homogenous composition and structure of the electrocatalysts prepared by ALD favor the exploration of structure-reactivity relationships and catalytic mechanisms. In this review, the mechanism, characteristics, and advantages of ALD in fabricating nanostructures are introduced first. Subsequently, the problems associated with existing electrocatalysts and a series of recently developed ALD strategies to enhance the activity and durability of electrocatalysts are presented. For example, the deposition of ultrafine Pt nanoparticles to increase the utilization and activity of Pt, fabrication of core–shell, overcoat, nanotrap, and other novel structures to protect the noble-metal nanoparticles and enhance the catalyst stability. In addition, ALD developments in synthesizing non-noble metallic electrocatalysts are summarized and discussed. Finally, based on the current studies, an outlook for the ALD application in the design and synthesis of electrocatalysts is presented.
基金the financial support from the National Natural Science Foundation of China(No.21905317)the financial support from the National Natural Science Foundation of China(No.91833301)the Youth Talent Promotion Project from China Association for Science and Technology。
文摘Piezocatalytic materials have been widely used for catalytic hydrogen evolution and purification of organic contaminants.However,most studies focus on nano-size and/or polycrystalline catalysts,suffering from aggregation and neutralization of internal piezoelectric field caused by polydomains.Here we report a single crystal ZnO of large size and few bulk defects crafted by a hydrothermal method for piezocatalytic hydrogen generation from pure water.It is noteworthy that single-side surface areas of both original as-prepared ZnO and Ga-doped ZnO bulk crystals are larger than 30 cm^(2).The high quality of ZnO and Ga-doped ZnO bulks are further uncovered by high-resolution transmission electron microscope(HRTEM),photoluminescence(PL)and X-ray diffraction(XRD).Remarkably,an outstanding hydrogen production rate of co-catalyst-free Ga-doped ZnO bulk crystal(i.e.,a maximum rate of 5915μmol h^(-1) m^(-2))is observed in pure water triggered by ultrasound in dark,which is over 100 times higher than that of its powder counterpart(i.e.,52.54μmol h^(-1) m^(-2)).The piezocatalytic performance of ZnO bulk crystal is systematically studied in terms of varied exposed crystal facet,thickness and conductivity.Different piezocatalytic performances are attributed to magnitude and distribution of piezoelectric potential,revealed by the finite element method(FEM)simulation.The density functional theory(DFT)calculations are employed to investigate the piezocatalytic hydrogen evolution process,indicating a strong H_(2)O adsorption and a low energy barrier for both H_(2)O dissociation and H2 generation on the stressed Znterminated(0001)ZnO surface.
基金financially supported by the National Natural Science Foundation of China(21771192)Major Program of Shandong Province Natural Science Foundation(ZR2017ZB0315)+3 种基金Program for Taishan Scholar of Shandong Province(ts201712019)the Fundamental Research Funds for the Central Universities(19CX05001A,18CX02053A)Qingdao Applied Basic Research Project(19-6-2-20-cg)Yankuang Group 2019 Science and Technology Program。
文摘The facile designs and fabrication of noble metal-free electrocatalysts are highly required to achieve multifunctional catalytic activity with excellent stability in Zn-air batteries,fuel cells and water splitting systems.Herein,a heterostructure engineering is applied to construct the high performance Co,Ncontaining carbon-based multifunctional electrocatalysts with the feature of isotype(i.e.n-n type Co_(2)N_(0.67)-BHPC)and anisotype(i.e.p-n type Co_(2)O_(3)-BHPC)heterojunctions for ORR,OER and HER.The nn type Co_(2)N_(0.67)-BHPC,in which biomass(e.g.mushroom)-derived hierarchical porous carbon(BHPC)incorporated with nonstoichiometric active species Co_(2)N_(0.67),is fabricated by using an in situ protective strategy of macrocyclic central Co-N_(4) from CoTPP(5,10,15,20-tetrakis(phenyl)porphyrinato cobalt)precursor through the intermolecularπ-πinteractions between CoTPP and its metal-free analogue H_(2) TPP.Meanwhile,an unprotected strategy of macrocyclic central Co-N_(4) from CoTPP can afford the anisotype Co_(2)O_(3)-BHPC p-n heterojunction.The as-prepared n-n type Co_(2)N_(0.67)-BHPC heterojunction exhibited a higher density of Co-based active sites with outstanding stability and more efficient charge transfer at the isotype heterojunction interface in comparison with p-n type Co_(2)O_(3)-BHPC heterojunction.Consequently,for ORR,Co_(2)N_(0.67)-BHPC exhibits the more positive onset and half-wave potentials of 0.93 and 0.86 V vs.RHE,respectively,superior to those of the commercial 20 wt%Pt/C and most of Cobased catalysts reported so far.To drive a current density of 10 mA cm^(-2),Co_(2)N_(0.67)-BHPC also shows the lower overpotentials of 0.34 and 0.21 V vs.RHE for OER and HER,respectively.Furthermore,the Zn-air battery equipped with Co_(2)N_(0.67)-BHPC displays higher maximum power density(109 mW cm^(-2))and charge-discharge cycle stability.Interestingly,the anisotype heterojunction Co_(2)O_(3)-BHPC as trifunctional electrocatalyst reveals evidently photoelectrochemical enhancement compared with the photostable Co_(2)N_(0.67)-BHPC.That is to say,isotype heterojunction material(n-n type Co^(2)N_(0.67)-BHPC)is equipped with better electrocatalytic performance than anisotype one(p-n type Co_(2)O_(3)-BHPC),but the opposite is true in photoelectrochemical catalysis.Meanwhile,the possible mechanism is proposed based on the energy band structures of the Co_(2)N_(0.67)-BHPC and Co_(2)O_(3)-BHPC and the cocatalyst effects.The present work provides much more possibilities to tune the electrocatalytic and photoelectrochemical properties of catalysts through a facile combination of heterostructure engineering protocol and macrocyclic central metal protective strategy.
文摘Transition metal Ni anchored in carbon material represents outstanding 2e^(-) oxygen reduction reaction(ORR)catalytic selectivity,but enhancing the adsorption strength of intermediate*OOH to promote its selectivity remains a major challenge.Herein,the NiX/Ni@NCHS composite catalyst with heteroatom doping(O,S)is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal Ni.With the synergistic effect of honeycomb structure and O atom,NiO/Ni@NCHS-700 exhibits an exceptional H_(2)O_(2)selectivity of above 89.1%across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte,and an unexpected H_(2)O_(2)production rate up to 1.47 mol gcat^(-1) h^(-1)@0.2 V,which outperforms most of the state-of-the-art catalyst.Meanwhile,NiS/Ni@NCHS exhibits excellent electrocatalytic performance,with 2e^(-) ORR selectivity of 91.3%,H_(2)O_(2)yield of 1.85@0.3 V.Density functional theory simulations and experiments results reveal that the heteroatom doping(O,S)method has been employed to regulate the adsorption strength of Ni atoms with*OOH,and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active site.The heteroatom doping method in this work provides significant guidance for promoting 2e^(-) ORR electrocatalysis to produce H_(2)O_(2).
基金support from the Czech Science Foundation,project EXPRO,No 19-27454Xsupport by the European Union under the REFRESH—Research Excellence For Region Sustainability and High-tech Industries project number CZ.10.03.01/00/22_003/0000048 via the Operational Programme Just Transition from the Ministry of the Environment of the Czech Republic+1 种基金Horizon Europe project EIC Pathfinder Open 2023,“GlaS-A-Fuels”(No.101130717)supported from ERDF/ESF,project TECHSCALE No.CZ.02.01.01/00/22_008/0004587).
文摘Green hydrogen from water splitting has emerged as a critical energy vector with the potential to spearhead the global transition to a fossil fuel-independent society.The field of catalysis has been revolutionized by single-atom catalysts(SACs),which exhibit unique and intricate interactions between atomically dispersed metal atoms and their supports.Recently,bimetallic SACs(bimSACs)have garnered significant attention for leveraging the synergistic functions of two metal ions coordinated on appropriately designed supports.BimSACs offer an avenue for rich metal–metal and metal–support cooperativity,potentially addressing current limitations of SACs in effectively furnishing transformations which involve synchronous proton–electron exchanges,substrate activation with reversible redox cycles,simultaneous multi-electron transfer,regulation of spin states,tuning of electronic properties,and cyclic transition states with low activation energies.This review aims to encapsulate the growing advancements in bimSACs,with an emphasis on their pivotal role in hydrogen generation via water splitting.We subsequently delve into advanced experimental methodologies for the elaborate characterization of SACs,elucidate their electronic properties,and discuss their local coordination environment.Overall,we present comprehensive discussion on the deployment of bimSACs in both hydrogen evolution reaction and oxygen evolution reaction,the two half-reactions of the water electrolysis process.
基金financially supported by the National Natural Science Foundation of China for Youths(No.21601067,21701057)the China Postdoctoral Science Foundation(No.2020 M673037)a project funded by the Priority Academic Program Development of the Jiangsu Higher Education Institutions。
文摘The high cost,scarcity,and poor stability of precious-metal-based catalysts have hindered their extensive application in energy conversion and storage.This stimulates the search for earth-abundant alternatives to replace noble metal electrocatalysts.Hence,in this study,we investigate a novel and low-cost bifunctional electrocatalyst consisting of ZnCoMnO_(4) anchored on nitrogen-doped graphene oxide(ZnCoMnO_(4)/N-rGO).Benefiting from the strong Co-N interaction in ZnCoMnO_(4) and the coupled conductive N-rGO,the catalysts exhibit high electrocatalytic activity.Moreover,density functional theory calculations support the dominant role of the strong Co-N electronic interaction,which leads to ZnCoMnO_(4)/N-rGO having more favorable binding energies with O2 and H_(2) O,resulting in fast reaction kinetics.The obtained ZnCoMnO_(4)/N-rGO electrocatalyst exhibits superb bifunctional activity,with a half-wave potential of 0.83 V for the oxygen reduction reaction and a low onset potential of 1.57 V for the oxygen evolution reaction in 0.1 M KOH solution.Furthermore,a Zn-air battery driven by the ZnCoMnO_(4)/N-rGO catalyst shows remarkable discharge/charge performance,with a power density of 138.52 mW cm^(-2) and longterm cycling stability for 48 h.This work provides a promising multifunctional electrocatalyst based on non-noble metals for the storage and conversion of renewable energy.
