Zinc-ion supercapacitors(ZISCs)have received considerable interest for energy storage because of their low cost,high safety,and minimal environmental impact.However,they have a low energy density and poor cycling perf...Zinc-ion supercapacitors(ZISCs)have received considerable interest for energy storage because of their low cost,high safety,and minimal environmental impact.However,they have a low energy density and poor cycling performance.The design of a better cathode material is needed to overcome these limitations.A simple method was used to synthesize binder-free electrochemically exfoliated carbon paper(EECP)which modifies the surface of the paper by introducing oxygen functional groups and thus improves its pseudocapacitance.When used in a Zn-ion supercapacitor(ZISC),an EECPbased cathode provides a large surface area and quick charge transfer.As a result,the ZISC had remarkable charge storage properties and had a dominant capacitive-type charge storage mechanism with 78.8%retention of capacity at 10 mV/s of the total storage.Furthermore,at 1 A/g,the EECP electrode had a maximum capacitance of 252.5 F/g.The EECP electrode retained 81.7%of its capacitance after 10000 cycles,indicating its promise for use in the growing renewable energy sector.A ZISC was also constructed using EECP as the positive electrode and Zn as the negative electrode with a 1 mol L^(−1) ZnSO_(4) electrolyte.It had a capacitance of 186.22 F/g at 1 A/g and a 97.01%retention rate after 10000 cycles.It also had an excellent energy density of 46.6 Wh/kg at a power density of 500.4 W/kg.The material is therefore suitable for use in high-rate next-generation ZISCs.展开更多
The nonchemically amplified(nonCA)polymer resists,including ionic and nonionic types,have achieved higher resolution and smaller line edge roughness(LER)than traditional chemically amplified ones.However,for polymer r...The nonchemically amplified(nonCA)polymer resists,including ionic and nonionic types,have achieved higher resolution and smaller line edge roughness(LER)than traditional chemically amplified ones.However,for polymer resists,chain entanglement is an inevitable limitation for the further reduction of LER.To overcome this problem,it is logical to apply the nonCA concept to molecule-based resists due to their advantages of monodispersity and small size.To date,only a few examples of ionic sulfonium salts-based nonCA molecular glass resists(nonCAMGRs)have been reported.They demonstrated high resolution and small LER well,but their electron beam sensitivity seemed less than ideal.To our knowledge,non-ionic sulfoxime oxime esters-based molecular resists were not reported yet,which leaves room for new round of more in-depth reserch on nonCAMGRs.Here,employing the excellent spirobixanthene backbone,we have first designed non-ionic sulfoxime oxime esters-based nonCAMGRs X4-NI-tf and X4-NI-tfb,for comparison,sulfonium salts-based nonCAMGRs X4-I-otfdm was designed.All exhibit favorable thermal properties(T_(d,5%)>200°C)and filmforming capabilities(RMSs<0.4 nm).Via EBL,X4-I-otfdm achieved higher resolution(16 nm,LER 1.4 nm)than X4-NI-tf and X4-NI-tfb(20 nm,LER 1.6 nm).But contrast curve revealed that the sensitivity of X4-NI-tf and X4-NI-tfb(D_(100):370 and 350μC/cm^(2))was significantly higher than X4-I-otfdm(D_(100):3300μC/cm^(2)),demonstrating that the sensitivity of sulfoxime oxime esters exceeds that of sulfonium salts and introduction of bromine can further enhance the sensitivity;based on above,X4-NI-tfb exhibited the lowest Z-factor and demonstrated the best overall performance.We believe that nonCAMGRs based on sulfoxime oxime esters represent a strong candidate for high-performance photoresists.展开更多
Conventional error cancellation approaches separate molecules into smaller fragments and sum the errors of all fragments to counteract the overall computational error of the parent molecules.However,these approaches m...Conventional error cancellation approaches separate molecules into smaller fragments and sum the errors of all fragments to counteract the overall computational error of the parent molecules.However,these approaches may be ineffective for systems with strong localized chemical effects,as fragmenting specific substructures into simpler chemical bonds can introduce additional errors instead of mitigating them.To address this issue,we propose the Substructure-Preserved Connection-Based Hierarchy(SCBH),a method that automatically identifies and freezes substructures with significant local chemical effects prior to molecular fragmentation.The SCBH is validated by the gas-phase enthalpy of formation calculation of CHNO molecules.Therein,based on the atomization scheme,the reference and test values are derived at the levels of Gaussian-4(G4)and M062X/6-31+G(2df,p),respectively.Compared to commonly used approaches,SCBH reduces the average computational error by half and requires only15%of the computational cost of G4 to achieve comparable accuracy.Since different types of local effect structures have differentiated influences on gas-phase enthalpy of formation,substituents with strong electronic effects should be retained preferentially.SCBH can be readily extended to diverse classes of organic compounds.Its workflow and source code allow flexible customization of molecular moieties,including azide,carboxyl,trinitromethyl,phenyl,and others.This strategy facilitates accurate,rapid,and automated computations and corrections,making it well-suited for high-throughput molecular screening and dataset construction for gas-phase enthalpy of formation.展开更多
Layered double hydroxides(LDHs)hold great promise as cathode materials for aqueous zinc-ion batteries(AZIBs).Nevertheless,they also face challenges of sluggish kinetics and rapid capacity loss.Herein,a conformational ...Layered double hydroxides(LDHs)hold great promise as cathode materials for aqueous zinc-ion batteries(AZIBs).Nevertheless,they also face challenges of sluggish kinetics and rapid capacity loss.Herein,a conformational entropy regulation strategy has been applied to surmount the shortcomings.A medium-entropy iron-based metal organic framework(MIL-88)derived NiCoFeInZnV-based layered double hydroxide with carbon loaded(ME-NiCoFeInZnV-LDH/C)has been first proposed and prepared with a designed method.The increased entropy optimizes electron conductivity and alleviates structure alteration and diffusion barrier during interactions with charge carriers,due to electron-induced effect and“cocktail”effect.Moreover,the nanosheet assembled hollow prismatic structures could homogenize flux distribution and electric field distribution.Therefore,the electrochemical kinetics,crystal structure stability,and activity could be dramatically improved.Leveraging the advantages of structure and composition regulation,Zn||ME-NiCoFeInZnV-LDH/C zinc battery delivers high specific capacities,rate performance,and cycling stability.This work proposes a novel and feasible medium-entropy strategy to prepare a high-performance cathode for advanced AZIBs,which is of prominent significance for the development of charge storage devices.展开更多
High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carb...High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.展开更多
Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and am...Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and amino acids.However,the complexity of multistep reaction routes and the presence of competing side reactions pose significant challenges,often leading to low yield and poor selectivity of target products.To substantially enhance the efficiency and selectivity of C-N coupling reactions,it is imperative to gain a thorough understanding of the underlying reaction mechanisms and to develop highly active photocatalysts.Such catalysts must be capable of effectively activating diverse substrates while maintaining an appropriate balance between the adsorption and desorption of carbon-and nitrogen-containing intermediates or radical species.In this review,we systematically summarize recent advances in photocatalytic C-N coupling for the production of amides and amino acids from waste plastic-and biomass-based feedstocks,with particular focus on catalyst selection,process design,control of reaction intermediates,and catalytic mechanisms.Furthermore,the technoeconomic feasibility and environmental impact of these C-N coupling reactions are evaluated using technoeconomic analysis and life-cycle assessment.Lastly,the current challenges and future prospects in this field are also discussed.This review aims to provide valuable insights for the development of high-efficiency photocatalytic C-N coupling reactions and to deepen the understanding of their catalytic mechanisms.展开更多
In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mi...In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.展开更多
The development of intrinsically conductive piezoresistive sensors with high strain tolerance has garnered significant interest.While elastomeric polymers exhibit excellent strain capabilities,their utility in sensing...The development of intrinsically conductive piezoresistive sensors with high strain tolerance has garnered significant interest.While elastomeric polymers exhibit excellent strain capabilities,their utility in sensing applications has been limited by inherent challenges such as high electrical resistivity,poor aging resistance,and interfacial incompatibility.To address these limitations,hydroxyl-terminated polybutadiene(HTPB)-based polyurethane was chemically modified with acetylferrocene-polyaniline conductive moieties to enhance charge transport properties.Remarkably,this covalent functionalization endowed the resulting ferrocene-polyaniline hybrid polyurethane(FPHP)with a conductivity of2.33 n A at 1 V bias while preserving piezoresistive functionality.The FPHP demonstrated exceptional mechanical-electrical performance,achieving 254% elongation at break with strain-dependent gauge factors of 7.28(0%-12.5% strain,R^(2)=0.9504)and 19.66(12.5%-35.0% strain,R^(2)=0.9929).Further characterization revealed a rapid 0.60 s response time and stability over 3500 strain-release cycles at compression strain,underscoring its durability under repetitive loading.The FPHP sensor was capable of monitoring various human movements and recognizing writing signals.These advances establish a materials design paradigm for fabricating flexible sensors that synergistically integrate high deformability,tunable sensitivity,and robust operational stability,positioning FPHP as a promising candidate for next-generation wearable electronics and soft robotics.展开更多
Abuse of chloramphenicol(CAP)could cause serious side effects to human health.Therefore,it is necessary to detect CAP residues in animal sourced food effectively.Here,the superiority(better stability,higher Apt-CAP lo...Abuse of chloramphenicol(CAP)could cause serious side effects to human health.Therefore,it is necessary to detect CAP residues in animal sourced food effectively.Here,the superiority(better stability,higher Apt-CAP loading efficiency,and higher CAP binding associated conformational change,etc.)of tetrahedral structure to double-chained structure for developing aptasensor was evaluated.Then,a self-assembled DNA tetrahedral structure-based electrochemical aptasensor targeting CAP was developed.Under the optimized conditions,the aptasensor exhibited high sensitivity toward CAP with a limit of detection(LOD)of 0.0676 ng/m L(linear range 0.19-387.76 ng/m L),and high selectivity against the structural analogs of CAP.Moreover,the recovery rate of CAP from spiked milk samples ranged from 100.57%to 101.69%,and only USD 1.34 is needed for detecting CAP in 1 sample.These results suggested the application potential of this aptasesor for detecting CAP in animal sourced foods.展开更多
Space exploration and manufacturing are of critical importance for scientific advancement,technological innovation,national security,and the acquisition of extraterrestrial resources.In view of this,chemical and biolo...Space exploration and manufacturing are of critical importance for scientific advancement,technological innovation,national security,and the acquisition of extraterrestrial resources.In view of this,chemical and biological nano-/micro-/meso-scale manufacturing provide complementary approaches to overcome key space exploration challenges by enabling the in-situ production of essential life-support materials,propellants,and other resources.This review examines the origin and historical evolution of space manufacturing and the latest advances across different environments—from orbital space stations and the lunar surface to Mars and asteroids.It is structured to present the current state of research,outline key manufacturing strategies and technologies,assess the technical and environmental challenges,and discuss emerging trends and future directions.Besides,the potential applications of emerging technologies such as synthetic biology and artificial intelligence in overcoming the limitations of microgravity,limited resources,and extreme conditions are discussed.Ultimately,this integrative review could serve to guide future development,from advancing space science and disruptive manufacturing to enabling interdisciplinary and application-level innovations.展开更多
Plant bacterial diseases cause significant harm to agricultural production because of their frequent,intermittent and regional outbreaks.Currently,chemical control is still a more effective method for bacterial diseas...Plant bacterial diseases cause significant harm to agricultural production because of their frequent,intermittent and regional outbreaks.Currently,chemical control is still a more effective method for bacterial disease.To develop new,efficient and safe antibacterial agrochemicals,we summarize the research progress of compounds with antibacterial activities in the past ten years,classify them according to their active skeletons,and discuss their structure-activity relationships and mechanisms of action.Finally,the development trend of antibacterial agrochemicals was prospected.This review provides valuable information for the development of antibacterial agrochemicals.展开更多
Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as pre...Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.展开更多
Glucose,ascorbic acid(AA),uric acid(UA),and dopamine(DA)are vital biomarkers whose dynamic concentrations correlate with critical diseases;however,multiplexed detection remains challenging for conventional electrochem...Glucose,ascorbic acid(AA),uric acid(UA),and dopamine(DA)are vital biomarkers whose dynamic concentrations correlate with critical diseases;however,multiplexed detection remains challenging for conventional electrochemical sensors because of their limited sensitivity and selectivity.Here,we present a millimeter-scale all-poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)organic electrochemical transistor(OECT)platform that integrates dual-mode sensing with enzyme/metal-free operation for ultrasensitive biomarker monitoring.By engineering polycrystalline PEDOT:PSS channels via H_2 SO_4 post-treatment,the device achieves record-high conductivity(about(2312.0±29.9)S·cm^(–1)),maximum transconductance(about(2.82±0.12)mS),and on/off ratio(about 210.0±7.8),enabling signal amplification at low gate voltages.The dual-mode strategy combines the selectivity of electrochemistry with the sensitivity of OECTs,realizing simultaneous detection of glucose,AA,UA,and DA with clinical-level sensitivity:detection limits down to 8 nmol·L^(–1)(glucose),0.5 nmol·L^(–1)(AA),5 nmol·L^(–1)(DA),and 0.5 nmol·L^(–1)(UA).Validation using human urine samples yielded recovery rates of 94%–114%.This flexible sensing platform provides a new pathway for the development of wearable biosensors for precision diagnostics.展开更多
In manganese electrolysis,electrochemical oscillations and manganese dendrite growth are typical nonlinear phenomena critical for energy consumption reduction.Nonetheless,existing research lacks a deep understanding o...In manganese electrolysis,electrochemical oscillations and manganese dendrite growth are typical nonlinear phenomena critical for energy consumption reduction.Nonetheless,existing research lacks a deep understanding of their underlying mechanisms.In this study,we systematically explored the evolution of anode electrochemical oscillations during manganese electrolysis and designed a square wave circuit to effectively suppress oscillations and dendrite growth while reducing energy consumption.A novel four-dimensional differential equation was introduced to explore the internal dynamic mechanisms of typical nonlinear behaviors.The experimental results showed that while the evolutionary patterns of current and potential oscillation signals were consistent,their waveform directions were opposite.The square wave current effectively suppressed both electrochemical oscillations and the growth of manganese dendrites.Furthermore,compared to direct current electrolysis,the square wave current improved the current efficiency by 3.6%and reduced the energy consumption by 0.32 kW·h·kg^(−1).展开更多
Photoelectrochemical CO_(2)reduction to multi-carbon products fuels remains challenged by inefficient C–C coupling and competing proton reduction reaction.Herein,we designed a cationic covalent organic framework(COF+...Photoelectrochemical CO_(2)reduction to multi-carbon products fuels remains challenged by inefficient C–C coupling and competing proton reduction reaction.Herein,we designed a cationic covalent organic framework(COF+)to create an electrostatic microenvironment that synergizes with CuPt alloy nanoparticles for selective ethylene/ethane production.By spatially decoupling CO_(2)enrichment from proton exclusion,the COF^(+)/CuPt interface simultaneously facilitates CO_(2)accessibility while impeding H+migration,suppressing the hydrogen evolution reaction(HER).This unique microenvironment stabilizes key anionic intermediates(*COO^(−),*OCCO^(−))and promotes*CO dimerization,steering electron transfer toward C–C coupling.The optimized system achieves a record-high Faradaic efficiency of 51.5%±5.3%for ethane and 10.6%±2.5%for ethylene with a total C2+yield exceeding 62%at−0.25 V vs.RHE and high stability(>300 min),representing the highest performance for photoelectrochemical CO_(2)reduction to ethane.The combined analyses of in situ spectroscopy and theoretical calculations reveal that electrostatic field effects lower the energy barrier for*OCCO formation while accelerating hydrogenation kinetics.Therefore,this work demonstrates that microenvironment modification of the active site by cationic covalent organic framework is a versatile strategy for solar-driven CO_(2)conversion into value-added hydrocarbons.展开更多
Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Here...Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Herein,the CuO_(x) nanowires supported Ru nanoclusters(Ru-CuO_(x))were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation.The prepared RuCuO_(x) shows a high ammonia yield rate of 2286.5μg h^(-1) cm^(-2) at-0.7 V vs.RHE and Faradaic efficiency(FE)of 80.1%at-0.4 V vs.RHE.Additionally,the nitrate conversion rate exceeds 90%at the potential range from-0.2 to-0.7 V vs.RHE,and the ammonia selectivity can reach 97.7%at-0.7 V vs.RHE in100 mg L^(-1) NaNO_(3) solution.The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO_(x) and accelerates the reconstruction of CuO_(x) to Cu but also promotes H2O dissociation to generate active hydrogen.Moreover.in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO_(3)RR.Density functional theory(DFT)calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step,thus improving the NO_(3)RR performance.展开更多
Supercapacitors represent one specific class of energy storage devices that bridge the gap between traditional capacitors and batteries.In current work,δ-MnO_(2) nanoflakes arrayed on electrochemically exfoliated gra...Supercapacitors represent one specific class of energy storage devices that bridge the gap between traditional capacitors and batteries.In current work,δ-MnO_(2) nanoflakes arrayed on electrochemically exfoliated graphene(EEG)nanosheets were easily made as one composited electrode material for boosting the charge storage performances of supercapacitors.Coupled with the fluent electron and ion transport from two-dimensional EEG nanosheets,the uniformly anchoredδ-MnO_(2) nanoflake arrays present high reversible capacity,superior cycling stability,and unique rate capability.As expected,the MnO_(2)/EEG-10 electrode delivers high specific capacitance of 190 F·g^(−1) at 0.2 A·g^(−1),and holds 97.3%of its initial capacitance after 10000 cycles at 5 A·g^(−1).Furthermore,an asymmetrical supercapacitor using MnO_(2)/EEG-10 as the positive electrode achieves an energy density of 17.7 W·h·kg^(−1) at a power density of 922.7 W·kg^(−1) with 82.9%capacity retention upon 10000 cycles at 5 A·g^(−1).This work highlights the facile fabrication of high-performance MnO_(2)/graphene composites with excellent structure stability using graphene nanosheets as the conductive matrix.展开更多
Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior perf...Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior performance of amorphous CuNi alloys for CO_(2)electrochemical reduction.By integrating machine learning forcefields for efficient structure generation and density functional theory for subsequent structural refinement and property calculations,we reveal the potential of these disordered systems to outperform their crystalline counterparts.Machine learning forcefields can generate a bulk structure containing a mixture of Cu and Ni atoms,resulting in enhanced catalytic performance.Effective screening of the amorphous surfaces is used to identify undercoordinated Cu and Ni sites in the amorphous structure to synergistically promote selective CO production and favor ethanol formation over ethylene via the stabilization of the*COCHO intermediate,resulting in significantly lower Gibbs free energy changes compared to the crystalline counterpart.The varying atomic coordination environments on amorphous surfaces promote both C–C bond formation and subsequent proton-electron transfer,leading to ethanol formation.These findings demonstrate the superior catalytic performance of amorphous CuNi,highlighting its potential for efficient and selective electroreduction of CO_(2).展开更多
Organic electrochemical transistors(OECTs)are promising for next-generation bioelectronics due to their high performance and biocompatibility.Nevertheless,they still face tremendous operational stability challenges du...Organic electrochemical transistors(OECTs)are promising for next-generation bioelectronics due to their high performance and biocompatibility.Nevertheless,they still face tremendous operational stability challenges due to the limited robustness of the organic mixed ionic-electronic conductor(OMIEC)channel.Here,by modulating the molecular weight(MW)of OMiEC,enhanced OECT and relevant circuit operation stabilities are demonstrated,showing more than 3,000,0o0 full cycles(~42 h)with less than 15%current variation in an OECT,and 150,000 cycles(~4 h)with less than 5%voltage variation in an OECT-based inverter,which are among the highest of reported OECT-based electronics.Specifically,p(g2T-T),a typical p-type OMIEC,with varying MW(7-43 kDa),is synthesized,where lower-MW p(g2T-T)(~9 kDa)exhibits superior device performance and cycling stability in OECTs,outperforming those in high-MW counterparts(>30 kDa).It is indicated that low-MW p(g2T-T)maintains higher volumetric capacitance,ordered orientation,and reduced swelling.Therefore,irreversible microstructural degradation is effectively avoided,along with better performance yield.Furthermore,MW regulation enables physiological signal sensing with high tolerance to body fluid environments for 7 days.These findings highlight MW modulation as a versatile approach to suppress excessive swelling,advancing the design of durable OECT-based electronics.展开更多
Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)...Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.展开更多
基金supported by National Natural Science Foundation of China(52472194)the Deanship of Research and Graduate Studies at King Khalid University through Large Research Project(RGP-2/687/46).
文摘Zinc-ion supercapacitors(ZISCs)have received considerable interest for energy storage because of their low cost,high safety,and minimal environmental impact.However,they have a low energy density and poor cycling performance.The design of a better cathode material is needed to overcome these limitations.A simple method was used to synthesize binder-free electrochemically exfoliated carbon paper(EECP)which modifies the surface of the paper by introducing oxygen functional groups and thus improves its pseudocapacitance.When used in a Zn-ion supercapacitor(ZISC),an EECPbased cathode provides a large surface area and quick charge transfer.As a result,the ZISC had remarkable charge storage properties and had a dominant capacitive-type charge storage mechanism with 78.8%retention of capacity at 10 mV/s of the total storage.Furthermore,at 1 A/g,the EECP electrode had a maximum capacitance of 252.5 F/g.The EECP electrode retained 81.7%of its capacitance after 10000 cycles,indicating its promise for use in the growing renewable energy sector.A ZISC was also constructed using EECP as the positive electrode and Zn as the negative electrode with a 1 mol L^(−1) ZnSO_(4) electrolyte.It had a capacitance of 186.22 F/g at 1 A/g and a 97.01%retention rate after 10000 cycles.It also had an excellent energy density of 46.6 Wh/kg at a power density of 500.4 W/kg.The material is therefore suitable for use in high-rate next-generation ZISCs.
基金supported by the National Natural Science Foundation of China(No.22278059,22174009,22078047)Fundamental Research Funds for the Central Universities(No.DUT24ZD119,DUT22LAB601 and DUT22LAB608).
文摘The nonchemically amplified(nonCA)polymer resists,including ionic and nonionic types,have achieved higher resolution and smaller line edge roughness(LER)than traditional chemically amplified ones.However,for polymer resists,chain entanglement is an inevitable limitation for the further reduction of LER.To overcome this problem,it is logical to apply the nonCA concept to molecule-based resists due to their advantages of monodispersity and small size.To date,only a few examples of ionic sulfonium salts-based nonCA molecular glass resists(nonCAMGRs)have been reported.They demonstrated high resolution and small LER well,but their electron beam sensitivity seemed less than ideal.To our knowledge,non-ionic sulfoxime oxime esters-based molecular resists were not reported yet,which leaves room for new round of more in-depth reserch on nonCAMGRs.Here,employing the excellent spirobixanthene backbone,we have first designed non-ionic sulfoxime oxime esters-based nonCAMGRs X4-NI-tf and X4-NI-tfb,for comparison,sulfonium salts-based nonCAMGRs X4-I-otfdm was designed.All exhibit favorable thermal properties(T_(d,5%)>200°C)and filmforming capabilities(RMSs<0.4 nm).Via EBL,X4-I-otfdm achieved higher resolution(16 nm,LER 1.4 nm)than X4-NI-tf and X4-NI-tfb(20 nm,LER 1.6 nm).But contrast curve revealed that the sensitivity of X4-NI-tf and X4-NI-tfb(D_(100):370 and 350μC/cm^(2))was significantly higher than X4-I-otfdm(D_(100):3300μC/cm^(2)),demonstrating that the sensitivity of sulfoxime oxime esters exceeds that of sulfonium salts and introduction of bromine can further enhance the sensitivity;based on above,X4-NI-tfb exhibited the lowest Z-factor and demonstrated the best overall performance.We believe that nonCAMGRs based on sulfoxime oxime esters represent a strong candidate for high-performance photoresists.
基金the support of the National Natural Science Foundation of China(22575230)。
文摘Conventional error cancellation approaches separate molecules into smaller fragments and sum the errors of all fragments to counteract the overall computational error of the parent molecules.However,these approaches may be ineffective for systems with strong localized chemical effects,as fragmenting specific substructures into simpler chemical bonds can introduce additional errors instead of mitigating them.To address this issue,we propose the Substructure-Preserved Connection-Based Hierarchy(SCBH),a method that automatically identifies and freezes substructures with significant local chemical effects prior to molecular fragmentation.The SCBH is validated by the gas-phase enthalpy of formation calculation of CHNO molecules.Therein,based on the atomization scheme,the reference and test values are derived at the levels of Gaussian-4(G4)and M062X/6-31+G(2df,p),respectively.Compared to commonly used approaches,SCBH reduces the average computational error by half and requires only15%of the computational cost of G4 to achieve comparable accuracy.Since different types of local effect structures have differentiated influences on gas-phase enthalpy of formation,substituents with strong electronic effects should be retained preferentially.SCBH can be readily extended to diverse classes of organic compounds.Its workflow and source code allow flexible customization of molecular moieties,including azide,carboxyl,trinitromethyl,phenyl,and others.This strategy facilitates accurate,rapid,and automated computations and corrections,making it well-suited for high-throughput molecular screening and dataset construction for gas-phase enthalpy of formation.
基金the funding support from the National Natural Science Foundation of China(Grant No.52202217,52471222)the Natural Science Foundation of Jilin Province(Grant No.YDZJ202201ZYTS375).
文摘Layered double hydroxides(LDHs)hold great promise as cathode materials for aqueous zinc-ion batteries(AZIBs).Nevertheless,they also face challenges of sluggish kinetics and rapid capacity loss.Herein,a conformational entropy regulation strategy has been applied to surmount the shortcomings.A medium-entropy iron-based metal organic framework(MIL-88)derived NiCoFeInZnV-based layered double hydroxide with carbon loaded(ME-NiCoFeInZnV-LDH/C)has been first proposed and prepared with a designed method.The increased entropy optimizes electron conductivity and alleviates structure alteration and diffusion barrier during interactions with charge carriers,due to electron-induced effect and“cocktail”effect.Moreover,the nanosheet assembled hollow prismatic structures could homogenize flux distribution and electric field distribution.Therefore,the electrochemical kinetics,crystal structure stability,and activity could be dramatically improved.Leveraging the advantages of structure and composition regulation,Zn||ME-NiCoFeInZnV-LDH/C zinc battery delivers high specific capacities,rate performance,and cycling stability.This work proposes a novel and feasible medium-entropy strategy to prepare a high-performance cathode for advanced AZIBs,which is of prominent significance for the development of charge storage devices.
基金the Natural Science Foundation of ZhejiangProvince(No.LZ24B020005)the National Natural Science Foundation of China(No.22071040)for financial support.
文摘High-sensitive quantitative determination of alpha-fetoprotein(AFP)is of crucial importance for early clinical diagnosis of cancers.Herein,an AuNPs-free electrochemical immunosensor(Ab1-Fc-COF)was prepared from a carboxylic group enriched COF by post-functionalization with detecting antibody(Ab1)and ferrocene(Fc),and used for electrochemical detection of AFP.Due to the small,homogeneous pore size of the COF,Ab1 with a big size was immobilized on the surface of the COF,while Fc with a small size was covalently modified both on the surface and in the pores of COF.The covalently immobilized Ab1 was quite stable and beneficial to specifically detect AFP biomarkers.Meanwhile,the enriched Fc molecules not only improved the conductivity of the COF,but also effectively transferred and amplified the electrochemical signal.This proposed immunosensor exhibited high sensitivity in detecting AFP with a detection limit of 0.39 pg/mL(S/N of 3:1)and a wide linear response range spanning from 1 pg/mL to 100 ng/mL when plotted against logarithmic concentrations.Furthermore,this immunosensor showed excellent selectivity,stability and reproducibility in the testing of real samples.This study presents an innovative prototype for construction of a precious metal-free,antibody-directly-immobilized,simple and stable electrochemical immunoprobe.
基金supported by the National Natural Science Foundation of China(Nos.22572141,22178266)Talent Program Fund of Tianjin University(Nos.0701321039,0903074107)supported by a grant from the Key Laboratory of Recycling and Eco-Treatment of Waste Biomass of Zhejiang Province(No.2024HZYB02)。
文摘Photocatalytic C-N coupling reactions using waste plastic-and biomass-based feedstocks with nitrogen-containing species have emerged as a promising route for the synthesis of high-value chemicals such as amides and amino acids.However,the complexity of multistep reaction routes and the presence of competing side reactions pose significant challenges,often leading to low yield and poor selectivity of target products.To substantially enhance the efficiency and selectivity of C-N coupling reactions,it is imperative to gain a thorough understanding of the underlying reaction mechanisms and to develop highly active photocatalysts.Such catalysts must be capable of effectively activating diverse substrates while maintaining an appropriate balance between the adsorption and desorption of carbon-and nitrogen-containing intermediates or radical species.In this review,we systematically summarize recent advances in photocatalytic C-N coupling for the production of amides and amino acids from waste plastic-and biomass-based feedstocks,with particular focus on catalyst selection,process design,control of reaction intermediates,and catalytic mechanisms.Furthermore,the technoeconomic feasibility and environmental impact of these C-N coupling reactions are evaluated using technoeconomic analysis and life-cycle assessment.Lastly,the current challenges and future prospects in this field are also discussed.This review aims to provide valuable insights for the development of high-efficiency photocatalytic C-N coupling reactions and to deepen the understanding of their catalytic mechanisms.
基金Financial support from National Key R&D Program of China (No.2023YFA1507203)National Natural Science Foundation of China (Nos.22371149 and 22188101)+3 种基金the Fundamental Research Funds for the Central Universities (No.63224098)Frontiers Science Center for New Organic Matter,Nankai University (No.63181206)Nankai University are gratefully acknowledgedthe Haihe Laboratory of Sustainable Chemical Transformations for financial support。
文摘In this study,electrochemical C-H carboxylation of benzylamines with CO_(2) was reported.This linear paired electrolysis system enables efficient and economical synthesis of value-added α-amino acids(α-AAs) under mild conditions.Various substituted benzylamines containing diverse functional groups and even highly reactive moieties,such as cyano,amide and alkene groups could be successfully transformed to the carboxylated products.Notably,this method proved to be applicable to the late-stage modification of biorelevant compounds,highlighting its potential for synthetic chemistry.Mechanistic studies such as radical trapping experiments,kinetic isotope effect(KIE) tests and cyclic voltammetry(CV) studies provided useful insight into this transformation.
文摘The development of intrinsically conductive piezoresistive sensors with high strain tolerance has garnered significant interest.While elastomeric polymers exhibit excellent strain capabilities,their utility in sensing applications has been limited by inherent challenges such as high electrical resistivity,poor aging resistance,and interfacial incompatibility.To address these limitations,hydroxyl-terminated polybutadiene(HTPB)-based polyurethane was chemically modified with acetylferrocene-polyaniline conductive moieties to enhance charge transport properties.Remarkably,this covalent functionalization endowed the resulting ferrocene-polyaniline hybrid polyurethane(FPHP)with a conductivity of2.33 n A at 1 V bias while preserving piezoresistive functionality.The FPHP demonstrated exceptional mechanical-electrical performance,achieving 254% elongation at break with strain-dependent gauge factors of 7.28(0%-12.5% strain,R^(2)=0.9504)and 19.66(12.5%-35.0% strain,R^(2)=0.9929).Further characterization revealed a rapid 0.60 s response time and stability over 3500 strain-release cycles at compression strain,underscoring its durability under repetitive loading.The FPHP sensor was capable of monitoring various human movements and recognizing writing signals.These advances establish a materials design paradigm for fabricating flexible sensors that synergistically integrate high deformability,tunable sensitivity,and robust operational stability,positioning FPHP as a promising candidate for next-generation wearable electronics and soft robotics.
基金supported by the National Nature Science Foundation of China(82174531)the Medicine and Health Science Technology Development Project of Shandong Province,China(202212060626).
文摘Abuse of chloramphenicol(CAP)could cause serious side effects to human health.Therefore,it is necessary to detect CAP residues in animal sourced food effectively.Here,the superiority(better stability,higher Apt-CAP loading efficiency,and higher CAP binding associated conformational change,etc.)of tetrahedral structure to double-chained structure for developing aptasensor was evaluated.Then,a self-assembled DNA tetrahedral structure-based electrochemical aptasensor targeting CAP was developed.Under the optimized conditions,the aptasensor exhibited high sensitivity toward CAP with a limit of detection(LOD)of 0.0676 ng/m L(linear range 0.19-387.76 ng/m L),and high selectivity against the structural analogs of CAP.Moreover,the recovery rate of CAP from spiked milk samples ranged from 100.57%to 101.69%,and only USD 1.34 is needed for detecting CAP in 1 sample.These results suggested the application potential of this aptasesor for detecting CAP in animal sourced foods.
基金supported by National Natural Science Foundation of China(22278241)a grant from the Institute Guo Qiang,Tsinghua University(2021GQG1016).
文摘Space exploration and manufacturing are of critical importance for scientific advancement,technological innovation,national security,and the acquisition of extraterrestrial resources.In view of this,chemical and biological nano-/micro-/meso-scale manufacturing provide complementary approaches to overcome key space exploration challenges by enabling the in-situ production of essential life-support materials,propellants,and other resources.This review examines the origin and historical evolution of space manufacturing and the latest advances across different environments—from orbital space stations and the lunar surface to Mars and asteroids.It is structured to present the current state of research,outline key manufacturing strategies and technologies,assess the technical and environmental challenges,and discuss emerging trends and future directions.Besides,the potential applications of emerging technologies such as synthetic biology and artificial intelligence in overcoming the limitations of microgravity,limited resources,and extreme conditions are discussed.Ultimately,this integrative review could serve to guide future development,from advancing space science and disruptive manufacturing to enabling interdisciplinary and application-level innovations.
基金The financial support from the National Natural Science Foundation of China (No.31972290)National Key Research and Development Program of China (No.2022YFD1700300)。
文摘Plant bacterial diseases cause significant harm to agricultural production because of their frequent,intermittent and regional outbreaks.Currently,chemical control is still a more effective method for bacterial disease.To develop new,efficient and safe antibacterial agrochemicals,we summarize the research progress of compounds with antibacterial activities in the past ten years,classify them according to their active skeletons,and discuss their structure-activity relationships and mechanisms of action.Finally,the development trend of antibacterial agrochemicals was prospected.This review provides valuable information for the development of antibacterial agrochemicals.
基金supported by the National Natural Sci-ence Foundation of China(Nos.22478263,22308230)Natural Science Foundation of Sichuan(No.2024NSF-SC1134)+2 种基金China Postdoctoral Science Foundation(No.2024T170612)111 center(B17030)the Fun-damental Research Funds for the Central Universities.
文摘Optically pure chiral chemicals are important building blocks with widespread applications across mul-tiple scientific and industrial do-mains such as in pharmaceuticals,agrochemicals,and food,especially acting as precursors to synthesize biodegradable polymers.As an al-ternative to fossil resources,renew-able lignocellulosic biomass has been used to access chiral chemicals,due to the versatile inherent stere-ostructures and multiple functional groups,such as hydroxyl,carbonyl,and phenyl ether groups.Typically,as the two main units of(hemi)cel-lulose components in lignocellulosic biomass,D-xylose and D-glucose bear multiple chiral centers(e.g.,2R-3S-4R for D-xylose and 2R-3S-4R-5R for D-glucose).Lignin bearsβ-O-4 linkages,exhibiting(R,S/S,R)or(R,R/S,S)stereocenters at the side-chainαandβcarbon atoms.The valorization of biomass into optical-ly pure chiral chemicals is vital for developing a more sustainable future.This review discuss-es the production of typical chiral chemicals derived from biomass through chemocatalysis,including lactones(e.g.,R/S-valerolactone),carboxylic acids(e.g.,D/L-glyceric acid,D/L-lactic acid),polyols(e.g.,tetrose),furans,oligosaccharides,and others.Two strategies are generally employed.One approach involves first producing achiral platform chemicals from biomass,followed by the introduction of asymmetric catalysts to reconstruct stereocenters.The second relates to selectively preserving one or more inherent stereocenters in the natural biomass structure during complex cascade reactions in which biomass feedstock acts as a“chi-ral pool",thus eliminating the establishment of stereocenter.The feedstock,methods em-ployed,and enantioselectivity and applications of the target chiral chemicals are discussed.Despite these advances,the synthesis of optically pure chemicals from biomass is still in its in-fancy.The coming decade presents both extraordinary challenges and opportunities in biomass-derived chiral chemistry.Future research should be focused on:(1)integrating well-established asymmetric catalysis techniques and methods with biomass’s inherent chiral pools,presenting an unprecedented opportunity to expand the chemical space of sustainable chiral compounds;(2)mastering polyfunctional complexity of chiral chemicals through holis-tic utilization of biomass’multichiral centers;(3)unlocking lignin’s stereochemical treasury that represents the next frontier in biomass valorization.
基金financially supported by the National Natural Science Foundation of China(Nos.52272214,52372082,52466013,52373184,and U24A20660)Jiangxi Provincial Natural Science Foundation(Nos.20242BAB26059,20232BAB204032,20252BAC200290,20252BEJ730349,and 20252BAC240326)Doctoral Start-Up Fund of Jiangxi Science&Technology Normal University(No.2024BSQD16)。
文摘Glucose,ascorbic acid(AA),uric acid(UA),and dopamine(DA)are vital biomarkers whose dynamic concentrations correlate with critical diseases;however,multiplexed detection remains challenging for conventional electrochemical sensors because of their limited sensitivity and selectivity.Here,we present a millimeter-scale all-poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate)(PEDOT:PSS)organic electrochemical transistor(OECT)platform that integrates dual-mode sensing with enzyme/metal-free operation for ultrasensitive biomarker monitoring.By engineering polycrystalline PEDOT:PSS channels via H_2 SO_4 post-treatment,the device achieves record-high conductivity(about(2312.0±29.9)S·cm^(–1)),maximum transconductance(about(2.82±0.12)mS),and on/off ratio(about 210.0±7.8),enabling signal amplification at low gate voltages.The dual-mode strategy combines the selectivity of electrochemistry with the sensitivity of OECTs,realizing simultaneous detection of glucose,AA,UA,and DA with clinical-level sensitivity:detection limits down to 8 nmol·L^(–1)(glucose),0.5 nmol·L^(–1)(AA),5 nmol·L^(–1)(DA),and 0.5 nmol·L^(–1)(UA).Validation using human urine samples yielded recovery rates of 94%–114%.This flexible sensing platform provides a new pathway for the development of wearable biosensors for precision diagnostics.
基金support from the Fundamental Research Funds for the Central Universities(2022CDJQY-005,2024CDJXY010)the Guangxi Science and Technology Program(AB24010229)is greatly acknowledged.
文摘In manganese electrolysis,electrochemical oscillations and manganese dendrite growth are typical nonlinear phenomena critical for energy consumption reduction.Nonetheless,existing research lacks a deep understanding of their underlying mechanisms.In this study,we systematically explored the evolution of anode electrochemical oscillations during manganese electrolysis and designed a square wave circuit to effectively suppress oscillations and dendrite growth while reducing energy consumption.A novel four-dimensional differential equation was introduced to explore the internal dynamic mechanisms of typical nonlinear behaviors.The experimental results showed that while the evolutionary patterns of current and potential oscillation signals were consistent,their waveform directions were opposite.The square wave current effectively suppressed both electrochemical oscillations and the growth of manganese dendrites.Furthermore,compared to direct current electrolysis,the square wave current improved the current efficiency by 3.6%and reduced the energy consumption by 0.32 kW·h·kg^(−1).
基金financial support from the National Natural Science Foundation of China(No.52273187)the Guangdong Basic and Applied Basic Research Foundation(2022A1515110372,2023A1515011306,2023A1515240077)+1 种基金the National Key Research and Development Program of China(2022YFA1502900)the Guangdong-Hong Kong Joint Laboratory for Preparation and Application of Ordered Structural Materials of Guangdong Province(2023B1212120011).
文摘Photoelectrochemical CO_(2)reduction to multi-carbon products fuels remains challenged by inefficient C–C coupling and competing proton reduction reaction.Herein,we designed a cationic covalent organic framework(COF+)to create an electrostatic microenvironment that synergizes with CuPt alloy nanoparticles for selective ethylene/ethane production.By spatially decoupling CO_(2)enrichment from proton exclusion,the COF^(+)/CuPt interface simultaneously facilitates CO_(2)accessibility while impeding H+migration,suppressing the hydrogen evolution reaction(HER).This unique microenvironment stabilizes key anionic intermediates(*COO^(−),*OCCO^(−))and promotes*CO dimerization,steering electron transfer toward C–C coupling.The optimized system achieves a record-high Faradaic efficiency of 51.5%±5.3%for ethane and 10.6%±2.5%for ethylene with a total C2+yield exceeding 62%at−0.25 V vs.RHE and high stability(>300 min),representing the highest performance for photoelectrochemical CO_(2)reduction to ethane.The combined analyses of in situ spectroscopy and theoretical calculations reveal that electrostatic field effects lower the energy barrier for*OCCO formation while accelerating hydrogenation kinetics.Therefore,this work demonstrates that microenvironment modification of the active site by cationic covalent organic framework is a versatile strategy for solar-driven CO_(2)conversion into value-added hydrocarbons.
基金the Natural Science Foundation of China(Grant No.NSFC-22072062,22202098)the Science and Technology Project of China Northern Rare Earth(BFXT-2023-D-0048 and BFXT-2022-D-0078)。
文摘Electrochemical nitrate reduction reaction(NO_(3)RR)is a sustainable strategy to treat wastewater and produce ammonia.However,it is still a challenge to prepare electrocatalysts with high activity and selectivity.Herein,the CuO_(x) nanowires supported Ru nanoclusters(Ru-CuO_(x))were fabricated via a three-step procedure for efficient nitrate conversion and highly selective ammonia generation.The prepared RuCuO_(x) shows a high ammonia yield rate of 2286.5μg h^(-1) cm^(-2) at-0.7 V vs.RHE and Faradaic efficiency(FE)of 80.1%at-0.4 V vs.RHE.Additionally,the nitrate conversion rate exceeds 90%at the potential range from-0.2 to-0.7 V vs.RHE,and the ammonia selectivity can reach 97.7%at-0.7 V vs.RHE in100 mg L^(-1) NaNO_(3) solution.The systematic characterizations clarify that the introduction of Ru not only regulates the electronic structure of CuO_(x) and accelerates the reconstruction of CuO_(x) to Cu but also promotes H2O dissociation to generate active hydrogen.Moreover.in-situ Raman spectroscopy reveals that the formed Ru-Cu is considered the actual active species during the NO_(3)RR.Density functional theory(DFT)calculations further prove that the obtained Ru-Cu facilitates the adsorption of nitrate and lowers the Gibbs free energy of the rate-determining step,thus improving the NO_(3)RR performance.
基金supported by Natural Science Foundation of Shandong Province(ZR2023ME155 and ZR2023ME085)the project of“20 Items of University”of Jinan(202228046)the Taishan Scholar Project of Shandong Province(tsqn202306226 and tsqn202211171).
文摘Supercapacitors represent one specific class of energy storage devices that bridge the gap between traditional capacitors and batteries.In current work,δ-MnO_(2) nanoflakes arrayed on electrochemically exfoliated graphene(EEG)nanosheets were easily made as one composited electrode material for boosting the charge storage performances of supercapacitors.Coupled with the fluent electron and ion transport from two-dimensional EEG nanosheets,the uniformly anchoredδ-MnO_(2) nanoflake arrays present high reversible capacity,superior cycling stability,and unique rate capability.As expected,the MnO_(2)/EEG-10 electrode delivers high specific capacitance of 190 F·g^(−1) at 0.2 A·g^(−1),and holds 97.3%of its initial capacitance after 10000 cycles at 5 A·g^(−1).Furthermore,an asymmetrical supercapacitor using MnO_(2)/EEG-10 as the positive electrode achieves an energy density of 17.7 W·h·kg^(−1) at a power density of 922.7 W·kg^(−1) with 82.9%capacity retention upon 10000 cycles at 5 A·g^(−1).This work highlights the facile fabrication of high-performance MnO_(2)/graphene composites with excellent structure stability using graphene nanosheets as the conductive matrix.
基金partially funded by EPSRC (EP/T022213/1, EP/W032260/1 and EP/P020194/1) via our membership of the UK’s HEC Materials Chemistry Consortium, which is funded by EPSRC (EP/L000202)part of the “Advancing Solid Interface and Lubricants by First Principles Material Design (SLIDE)” project that has received funding from the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation program (Grant agreement No. 865633)
文摘Amorphous materials represent a promising platform for advancing CO_(2)electrochemical reduction due to their inherently diverse coordination environments.In this study,we demonstrate computationally the superior performance of amorphous CuNi alloys for CO_(2)electrochemical reduction.By integrating machine learning forcefields for efficient structure generation and density functional theory for subsequent structural refinement and property calculations,we reveal the potential of these disordered systems to outperform their crystalline counterparts.Machine learning forcefields can generate a bulk structure containing a mixture of Cu and Ni atoms,resulting in enhanced catalytic performance.Effective screening of the amorphous surfaces is used to identify undercoordinated Cu and Ni sites in the amorphous structure to synergistically promote selective CO production and favor ethanol formation over ethylene via the stabilization of the*COCHO intermediate,resulting in significantly lower Gibbs free energy changes compared to the crystalline counterpart.The varying atomic coordination environments on amorphous surfaces promote both C–C bond formation and subsequent proton-electron transfer,leading to ethanol formation.These findings demonstrate the superior catalytic performance of amorphous CuNi,highlighting its potential for efficient and selective electroreduction of CO_(2).
基金supported by the National Key R&D Program of China(2024YFB3211600)the National Natural Science Foundation of China(Nos.62273073,52273316)+4 种基金the National Key R&D Program of China(2023YFC2411800,2022YFE0134800)the Natural Science Foundation of Sichuan(2025ZNSFSC0515)Chengdu Science Technology Bureau(2023-YF06-00028-HZ)and the Fundamental Research Funds for the Central Universities(ZYGX2025TS009,ZYGX2024XJ029,ZYGX2024XJ031)Sci-entific Research Innovation Capability Support Project for Young Faculty(ZYGXQNJSKYCXNLZCXM-M1P).
文摘Organic electrochemical transistors(OECTs)are promising for next-generation bioelectronics due to their high performance and biocompatibility.Nevertheless,they still face tremendous operational stability challenges due to the limited robustness of the organic mixed ionic-electronic conductor(OMIEC)channel.Here,by modulating the molecular weight(MW)of OMiEC,enhanced OECT and relevant circuit operation stabilities are demonstrated,showing more than 3,000,0o0 full cycles(~42 h)with less than 15%current variation in an OECT,and 150,000 cycles(~4 h)with less than 5%voltage variation in an OECT-based inverter,which are among the highest of reported OECT-based electronics.Specifically,p(g2T-T),a typical p-type OMIEC,with varying MW(7-43 kDa),is synthesized,where lower-MW p(g2T-T)(~9 kDa)exhibits superior device performance and cycling stability in OECTs,outperforming those in high-MW counterparts(>30 kDa).It is indicated that low-MW p(g2T-T)maintains higher volumetric capacitance,ordered orientation,and reduced swelling.Therefore,irreversible microstructural degradation is effectively avoided,along with better performance yield.Furthermore,MW regulation enables physiological signal sensing with high tolerance to body fluid environments for 7 days.These findings highlight MW modulation as a versatile approach to suppress excessive swelling,advancing the design of durable OECT-based electronics.
基金supported by the National Natural Science Foundation of China(Grant Nos.52478351,52208329)the Shenzhen Science and Technology Innovation Commission(Grant No.JCYJ20240813143306009)support is gratefully acknowledged.
文摘Polymer-modified bentonite(PMB)is much more effective at containing chemically aggressive liquids than conventional bentonite.The PMB manufacturing process typically utilizes natural,high-quality sodium bentonite(NaB)owing to its excellent hydrophilicity and swelling capacity.However,calcium bentonite(CaB),which is much more abundant worldwide,is rarely used for containment applications owing to its poor hydrophilicity.This study proposed a polymerization method that transforms sodium-activated calcium bentonite(NCB)into PMB to achieve low hydraulic conductivity(k)to aggressive liquids.The mechanism for its low k was revealed through characterization techniques and analyses(e.g.X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),scanning electron microscopy(SEM),and Brunauer-Emmett-Teller(BET)).The results showed that the PMB had a small amount of polymer elution(indicating better interface stability)and thus exhibited excellent barrier properties under chemically aggressive conditions,with the k of<10^(-11) m/s for 0.6 mol/L NaCl solution,which is four orders of magnitude lower than that of the NCB(k=3×10^(-7) m/s).Various microscopic analyses indicated that the selected monomers were successfully polymerized,and intercalated into and grafted onto the montmorillonite layers of bentonite.The formed polymer network increased the swelling capability of PMB granules,decreased the pore size,and created narrow and tortuous flow pathways leading to a very low k to aggressive liquids.
