Engineering high‐performance and low‐cost bifunctional catalysts for H_(2)(hydrogen evolution reaction[HER])and O_(2)(oxygen evolution reaction[OER])evolution under industrial electrocatalytic conditions remains cha...Engineering high‐performance and low‐cost bifunctional catalysts for H_(2)(hydrogen evolution reaction[HER])and O_(2)(oxygen evolution reaction[OER])evolution under industrial electrocatalytic conditions remains challenging.Here,for the first time,we use the stronger electronegativity of a rare‐Earth yttrium ion(Y^(3+))to induce in situ NiCo‐layered double‐hydroxide nanosheets from NiCo foam(NCF)treated by a dielectric barrier discharge plasma NCF(PNCF),and then obtain nitrogen‐doped YNiCo phosphide(N‐YNiCoP/PNCF)after the phosphating process using radiofrequency plasma in nitrogen.The obtained NYNiCoP/PNCF has a large specific surface area,rich heterointerfaces,and an optimized electronic structure,inducing high electrocatalytic activity in HER(331mV vs.2000mA cm^(−2))and OER(464mV vs.2000mA cm^(−2))reactions in 1MKOH electrolyte.X‐ray absorption spectroscopy and density functional theory quantum chemistry calculations reveal that the coordination number of CoNi decreased with the incorporation of Y atoms,which induce much shorter bonds of Ni and Co ions and promote long‐term stability of N‐YNiCoP in HER and OER under the simulated industrial conditions.Meanwhile,the CoN‐YP_(5)heterointerface formed by plasma N‐doping is the active center for overall water splitting.This work expands the applications of rare‐Earth elements in engineering bifunctional electrocatalysts and provides a new avenue for designing highperformance transition‐metal‐based catalysts in the renewable energy field.展开更多
Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are ...Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors.展开更多
Sustainable ammonia synthesis at ambient conditions that relies on renewable sources of energy and feedstocks is globally sought to replace the Haber-Bosch process.Here,using nitrogen and water as raw materials,a nont...Sustainable ammonia synthesis at ambient conditions that relies on renewable sources of energy and feedstocks is globally sought to replace the Haber-Bosch process.Here,using nitrogen and water as raw materials,a nonthermal plasma catalysis approach is demonstrated as an effective powerto-chemicals conversion strategy for ammonia production.By sustaining a highly reactive environment,successful plasma-catalytic production of NH_(3) was achieved from the dissociation of N_(2) and H_(2)O under mild conditions.Plasma-induced vibrational excitation is found to decrease the N_(2) and H_(2)O dissociation barriers,with the presence of matched catalysts in the nonthermal plasma discharge reactor contributing significantly to molecular dissociation on the catalyst surface.Density functional theory calculations for the activation energy barrier for the dissociation suggest that ruthenium catalysts supported on magnesium oxide exhibit superior performance over other catalysts in NH_(3) production by lowering the activation energy for the dissociative adsorption of N_(2) down to 1.07 eV.The highest production rate,2.67 mmol gcat.^(-1) h^(-1),was obtained using ruthenium catalyst supported on magnesium oxide.This work highlights the potential of nonthermal plasma catalysis for the activation of renewable sources to serve as a new platform for sustainable ammonia production.展开更多
Surface functionalization or modification to introduce more oxygen-containing functional groups to biochar is an effective strategy for tuning the physicochemical properties and promoting follow-up applications.In thi...Surface functionalization or modification to introduce more oxygen-containing functional groups to biochar is an effective strategy for tuning the physicochemical properties and promoting follow-up applications.In this study,non-thermal plasma was applied for biochar surface carving before being used in contaminant removal and energy storage applications.The results showed that even a low dose of plasma exposure could introduce a high number density of oxygen-functional groups and enhance the hydrophilicity and metal affinity of the pristine biochar.The plasma-treated biochar enabled a faster metal-adsorption rate and a 40%higher maximum adsorption capacity of heavy metal ion Pb^(2+).Moreover,to add more functionality to biochar surface,biochar with and without plasma pre-treatment was activated by KOH at a temperature of 800℃.Using the same amount of KOH,the plasma treatment resulted in an activated carbon product with the larger BET surface area and pore volume.The performance of the treated activated carbon as a supercapacitor electrode was also substantially improved by>30%.This study may provide guidelines for enhancing the surface functionality and application performances of biochar using non-thermal-based techniques.展开更多
Recent studies have shown the in vitro neuro-protective functions of atmospheric pressure plasma(APP)against multiple pathological injuries during ischaemic stroke(IS).However,whether APP treatment exerts a therapeuti...Recent studies have shown the in vitro neuro-protective functions of atmospheric pressure plasma(APP)against multiple pathological injuries during ischaemic stroke(IS).However,whether APP treatment exerts a therapeutic effect on a rat IS model remains unclear.Here,on the basis of needle-to-ring dielectric barrier discharge,an atmospheric pressure plasma jet(APPJ)was designed,with the Helium as the working gas which was driven by a sinusoidal voltage.Then,the treatment conditions were optimised for IS rat model treatment and the characteristics of this APPJ were further diagnosed.Subsequently,the rat IS model was established through 90 min middle cerebral artery occlusion(MCAO),and plasma was intermittently inhaled by rats via the nasal cavity for a 2 min period at 60 min of MCAO process.The therapeutic effects of this plasma jet device were then evaluated using biomedical analyses.According to our results,intermittent APP inhalation in the MCAO rats increased the serum NO content,improved the neurological function,enhanced regional cerebral blood flow,lowered brain infarction,and reduced the cell apoptosis in brain tissues of MCAO rats.Collectively,our data provides a novel potential strategy for IS treatment by using atmospheric-pressure plasma inhalation.展开更多
Methanol oxidation reaction(MOR),the key reaction for clean energy generation in fuel cells,is kinetically sluggish and short-lasting because of insufficient catalytic activity and stability of the common Pt-based ele...Methanol oxidation reaction(MOR),the key reaction for clean energy generation in fuel cells,is kinetically sluggish and short-lasting because of insufficient catalytic activity and stability of the common Pt-based electrocatalysts.Ordered Pt alloy structures which promise to surmount these issues,are challenging and impractical to fabricate using common high-temperature annealing.To address the urgent need for simple and rapid synthesis methods for such alloys,here we report the versatile plasma-assisted thermal annealing synthesis of a robust electrocatalyst with PtFe alloys supported on N-doped carbon nanotubes(denoted as PtFe@NCNT-P).Benefiting from the reactive plasma-specific effects,the PtFe@NCNT-P electrocatalyst features ultrafine PtFe alloy nanoparticles(mean size~2.88 nm,ordered degree~87.07%)and ultrathin N-doped carbon(NC)shells(0.3–0.7 nm),leading to the excellent catalytic activity and stability toward MOR.The catalyst shows the specific and mass activities of 3.99 mA/cm^(2)and 2,148.5 mA/mg,which are 7.82 and 7.41 times higher than those for commercial Pt/C(0.51 mA/cm^(2),290 mA/mg),and 2.18 and 2.59 times higher compared to the plasma-untreated PtFe@NCNT(1.83 mA/cm2,829.5 mA/mg),respectively.The PtFe@NCNT-P further exhibits extraordinary stability during the long-term chronoamperometry test and 1,000-cycle cyclic voltammetry scanning,much better compared to PtFe@NCNT samples even after the longer thermal annealing.These findings show great potential of the plasma-enabled synthesis of high-performance carbon-supported metallic electrocatalysts for the emerging clean energy technologies.展开更多
Two Minkowski functionals were tested in the capacity of morphological descriptors to quantitatively compare the arrays of vertically-aligned graphene flakes grown on smooth and nanoporous alumina and silica surfaces....Two Minkowski functionals were tested in the capacity of morphological descriptors to quantitatively compare the arrays of vertically-aligned graphene flakes grown on smooth and nanoporous alumina and silica surfaces. Specifically, the Euler-Poincaré characteristic and fractal dimension graphs were used to characterize the degree of connectivity and order in the systems, i.e. in the graphene flake patterns of petal-like and tree-like morphologies on solid substrates, and meshlike patterns (networks) grown on nanoporous alumina treated in low-temperature inductivelycoupled plasma. It was found that the Minkowski functionals return higher connectivity and fractal dimension numbers for the graphene flakepatterns with more complex morphologies, and indeed can be used as morphological descriptors to differentiate among various configurations of vertically-aligned graphene flakes grown on surfaces.展开更多
A spectrophotometric technique is developed to simultaneously quantify nitrate and nitrite in plasma treated water.The measurement is based on examining the inflection points(wavelengths)in the derivative absorbance o...A spectrophotometric technique is developed to simultaneously quantify nitrate and nitrite in plasma treated water.The measurement is based on examining the inflection points(wavelengths)in the derivative absorbance of the nitrate or nitrite solution.At the inflection points of the pure nitrate solution,the derivative absorbance is zero and independent of the nitrate’s concentration,and thus the nitrite’s concentration in a mixed nitrate and nitrite solution can be obtained by using the Beer’s law at these points.The nitrate’s concentration can also be achieved from the inflection points of nitrite in the same manner.The relation between the tested substance’s(nitrate or nitrite)concentration and the second-or the third-order absorbances is obtained at these inflection points.Test measurements for mixed aqueous solutions of nitrate and nitrite with or without hydrogen peroxide confirm the reliability of this technique.We applied this technique to quantify the nitrate and nitrite generated in air plasma treated aqueous solutions.The results indicate that both nitrate and nitrite concentrations increase with the plasma treatment time,and the nitrite species is found to be generated prior to the nitrate species in the air plasma treated aqueous solution.Moreover,the production rate of total nitrogen species is independent of the solutions’p H value.These results are relevant to diverse applications of plasma activated solutions in materials processing,biotechnology,medicine and other fields.展开更多
Converting CO_(2) into high‐value fuels and chemicals by renewable‐electricitypowered electrochemical CO_(2) reduction reaction(CRR)is a viable approach toward carbon‐emissions‐neutral processes.Unlike the thermoc...Converting CO_(2) into high‐value fuels and chemicals by renewable‐electricitypowered electrochemical CO_(2) reduction reaction(CRR)is a viable approach toward carbon‐emissions‐neutral processes.Unlike the thermocatalytic hydrogenation of CO_(2) at the solid‐gas interface,the CRR takes place at the three‐phase gas/solid/liquid interface near the electrode surface in aqueous solution,which leads to major challenges including the limited mass diffusion of CO_(2) reactant,competitive hydrogen evolution reaction,and poor product selectivity.Here we critically examine the various methods of surface and interface engineering of the electrocatalysts to optimize the microenvironment for CRR,which can address the above issues.The effective modification strategies for the gas transport,electrolyte composition,controlling intermediate states,and catalyst engineering are discussed.The key emphasis is made on the diverse atomic‐precision modifications to increase the local CO_(2) concentration,lower the energy barriers for CO_(2) activation,decrease the H2O coverage,and stabilize intermediates to effectively control the catalytic activity and selectivity.The perspectives on the challenges and outlook for the future applications of three‐phase interface engineering for CRR and other gasinvolving electrocatalytic reactions conclude the article.展开更多
The aqueous phase hydrogen peroxide(H_(2)O_(2aq))produced from the plasma-liquid interactions can directly or synergistically(with other substances)affect the liquid chemistry,and therefore it is important to unfold t...The aqueous phase hydrogen peroxide(H_(2)O_(2aq))produced from the plasma-liquid interactions can directly or synergistically(with other substances)affect the liquid chemistry,and therefore it is important to unfold the H_(2)O_(2aq)formation mechanism.However,up to now,a consensus on the H_(2)O_(2aq)formation mechanism is not reached.This review aims to survey the recent advances on the understanding of the H_(2)O_(2aq)formation mechanism in the system of a direct current discharge plasma operated over a liquid electrode.Theoretical and experimental analyses indicate that the recombination of dissolved OH radicals(OHaq)is the dominant process for the H_(2)O_(2aq)formation,while the purported plasma-induced photolysis of water and the dissolution of gaseous H_(2)O_(2)are ruled out.展开更多
Heterostructure engineering holds exceptional promise for the development of high-performance electrocatalysts for overall water splitting.However,production of inexpensive and high-efficiency bifunctional electrocata...Heterostructure engineering holds exceptional promise for the development of high-performance electrocatalysts for overall water splitting.However,production of inexpensive and high-efficiency bifunctional electrocatalysts remains a challenge.Herein,we demonstrate a simple method to synthesize a paper-mulberry(Broussonetia papyrifera)-inspired Co_(9)S_(8)@CoNi_(2)S_(4)/nickel foam(Co_(9)S_(8)@CoNi_(2)S_(4)/NF)heterojunction with high catalytic activity and stability.The process involves in situ growth of NiCo layered double hydroxide and in situ derivatization of ZIF-67,followed by the S heteroatom doping.The Co_(9)S_(8)@CoNi_(2)S_(4)/NF benefits from the heterostructure and functional advantages of multidimensional building blocks including one-dimensional(1D)nanowires,2D nanosheets and nanoparticles.The optimized Co_(9)S_(8)@CoNi_(2)S_(4)/NF heterojunction with 10% sulphur content reveals excellent electrocatalytic activity with the lower overpotentials of 68 mV for hydrogen evolution reaction(HER)and 170 mV for oxygen evolution reaction(OER)at 10 mA cm^(-2) in the 1.0 mol L^(-1) KOH solution,which is superior to the recently reported transition metal based electrocatalysts.The outstanding performance is attributed to the strong interface coupling between CoNi_(2)S_(4) and Co_(9)S_(8),the advantage of multidimensional structure and the customized electronic structure.The density functional theory suggests that the interface between Co_(9)S_(8) and CoNi_(2)S_(4) optimizes the adsorption of the multiple intermediates and further facilitates water splitting kinetics.This work offers a generic approach for heterostructure engineering design of highperformance catalytic system applications.展开更多
Dual argon plasmas ignited by one direct current power source are used to treat an aqueous solution of hydrogen tetrachloroaurate-(Ⅲ)trihydrate(HAuCl_(4)·3H_(2)O)which is contained in an H-type electrochemical c...Dual argon plasmas ignited by one direct current power source are used to treat an aqueous solution of hydrogen tetrachloroaurate-(Ⅲ)trihydrate(HAuCl_(4)·3H_(2)O)which is contained in an H-type electrochemical cell.The solution contained in one cell acts as a cathode,and in the other as an anode.Experiments are carried out to directly visualize the formation process of gold nanoparticles(Au NPs)in separated cells of the H-type electrochemical reactor.The results and analyzes suggest that hydrogen peroxide and hydrated electrons generated from the plasma-liquid interactions play the roles of reductants in the solutions,respectively.Hydrogen peroxide can be generated in the case of the liquid being a cathode or an anode,while most of hydrated electrons are formed in the case of the liquid being an anode.Therefore,the reduction of the AuCl_(4)−ions is mostly attributed to the hydrogen peroxide as the liquid acts as a cathode,while to the hydrogen peroxide and hydrated electrons as the liquid acts as an anode.Moreover,the p H value of the solution can be used to tune the formation processes and final form of the Au NPs due to its mediation of reductants.展开更多
In this work,a portable floating-electrode dielectric barrier discharge(FE-DBD)device is designed with a rechargeable battery as the power supply.The characteristics of the FE-DBD with a metal electrode and human hand...In this work,a portable floating-electrode dielectric barrier discharge(FE-DBD)device is designed with a rechargeable battery as the power supply.The characteristics of the FE-DBD with a metal electrode and human hand are studied and compared.The human contact safety is verified by calculating the current through the human body based on the equivalent circuit model.Escherichia coli inactivation experiments confirm the efficacy of the FE-DBD device in the envisaged applications.展开更多
Non-thermal plasma exhibits unique advan-tages in biomass conversion for the sustainable production of higher-value energy carriers.Different homogeneous catalysts are usually required for plasma-enabled biomass lique...Non-thermal plasma exhibits unique advan-tages in biomass conversion for the sustainable production of higher-value energy carriers.Different homogeneous catalysts are usually required for plasma-enabled biomass liquefaction to achieve time-and energy-efficient conver-sions.However,the effects of such catalysts on the plasma-assisted liquefaction process and of the plasma on those catalysts have not been thoroughly studied.In this study,an electrical discharge plasma is employed to promote the direct liquefaction of sawdust in a mixture of polyethylene glycol 200 and glycerol.Three commonly used chemicals,sulfuric acid,nitric acid and sodium p-toluene sulfate,were selected as catalysts.The effects of the type of catalyst and concentration on the liquefaction yield were examined;further,the roles of the catalysts in the plasma liquefaction process have been discussed.The results showed that the liquefaction yield attains a value of 90%within 5 min when 1%sulfuric acid was employed as the catalyst.Compared with the other catalysts,sulfuric acid presents the highest efficiency for the liquefaction of sawdust.It was observed that hydrogen ions from the catalyst were primarily responsible for the significant thermal effects on the liquefaction system and the generation of large quantities of active species;these effects directly con-tributed to a higher efficacy of the plasma-enabled liquefaction process.展开更多
The quantification of hydrogen peroxide(H_(2)O_(2))generated in the plasma-liquid interactions is of great importance,since the H_(2)O_(2)species is vital for the applications of the plasma-liquid system.Herein,we rep...The quantification of hydrogen peroxide(H_(2)O_(2))generated in the plasma-liquid interactions is of great importance,since the H_(2)O_(2)species is vital for the applications of the plasma-liquid system.Herein,we report on in situ quantification of the aqueous H_(2)O_(2)(H_(2)O_(2)aq)using a colorimetric method for the DC plasma-liquid systems with liquid as either a cathode or an anode.The results show that the H_(2)O_(2)aqyield is 8-12 times larger when the liquid acts as a cathode than when the liquid acts as an anode.The conversion rate of the gaseous OH radicals to H_(2)O_(2)aqis 4-6 times greater in the former case.However,the concentrations of dissolved OH radicals for both liquid as cathode and anode are of the same order of tens of n M.展开更多
Cellulose macrofibers (MFs) are gaining increasing interest as natural and biodegradable alternatives to fossil-derived polymers for both structural and functional applications. However, simultaneously achieving their...Cellulose macrofibers (MFs) are gaining increasing interest as natural and biodegradable alternatives to fossil-derived polymers for both structural and functional applications. However, simultaneously achieving their exceptional mechanical performance and desired functionality is challenging and requires complex processing. Here, we reported a one-step approach using a tension-assisted twisting (TAT) technique for MF fabrication from bacterial cellulose (BC). The TAT stretches and aligns BC nanofibers pre-arranged in hydrogel tubes to form MFs with compactly assembled structures and enhanced hydrogen bonding among neighboring nanofibers. The as-prepared BC MFs exhibited a very high tensile strength of 1 057 MPa and exceptional lifting capacity (over 340 000 when normalized by their own weight). Moreover, due to the volume expansion of BC nanofibers upon water exposure, BC MFs quickly harvested energy from environmental moisture to untwist the bundled networks, thus generating a torsional spinning with a peak rotation speed of 884 r/(min·m). The demonstrated rapid and intense actuation response makes the MFs ideal candidates for diverse humidity-response-based applications beyond advanced actuators, remote rain indicators, intelligent switches, and smart curtains.展开更多
Low-value,renewable,carbon-rich resources,with different biomass feedstocks and their derivatives as typical examples,represent virtually inexhaustive carbon sources and carbon-related energy on Earth.Upon conversion ...Low-value,renewable,carbon-rich resources,with different biomass feedstocks and their derivatives as typical examples,represent virtually inexhaustive carbon sources and carbon-related energy on Earth.Upon conversion to higher-value forms(referred to as“up-carbonization”here),these abundant feedstocks provide viable opportunities for energy-rich fuels and sustainable platform chemicals production.However,many of the current methods for such up-carbonization still lack sufficient energy,cost,and material efficiency,which affect their economics and carbon-emissions footprint.With external electricity precisely delivered,discharge plasmas enable many stubborn reactions to occur under mild conditions,by creating locally intensified and highly reactive environments.This technology emerges as a novel,versatile technology platform for integrated or stand-alone conversion of carbon-rich resources.The plasma-based processes are compatible for integration with increasingly abundant and cost-effective renewable electricity,making the whole conversion carbon-neutral and further paving the plasma-electrified upcarbonization to be performance-,environment-,and economics-viable.Despite the chief interest in this emerging area,no review article brings together the state-of-the-art results from diverse disciplines and underlies basic mechanisms and chemistry underpinned.As such,this review aims to fill this gap and provide basic guidelines for future research and transformation,by providing an overview of the application of plasma techniques for carbon-rich resource conversion,with particular focus on the perspective of discharge plasmas,the fundamentals of why plasmas are particularly suited for upcarbonization,and featured examples of plasma-enabled resource valorization.With parallels drawn and specificity highlighted,we also discuss the technique shortcomings,current challenges,and research needs for future work.展开更多
Plasma is an ionized gas.It is typically formed at high temperature.As a result of both the development of bow-temperature plasma sources and a better understanding of complex plasma phenomena over the last decade,&qu...Plasma is an ionized gas.It is typically formed at high temperature.As a result of both the development of bow-temperature plasma sources and a better understanding of complex plasma phenomena over the last decade,"plasma medicine"has become a booming interdisciplinary research topic of growing importance that explores enormous opportunities at the interface of chemistry,plasma physics,and biomedical sciences with engineering.This review presents the latest development in plasma medicine in the area of the central nervous system and aims to introduce cutting-edge plasma medicine to clinical and translational medical researchers and practitioners.展开更多
In recent years,translational plasma medicine(TPM),as a novel application area of plasmas,has attracted much attention of experts from both academic and clinical fields.State-of-the-art of the lab-scale research and c...In recent years,translational plasma medicine(TPM),as a novel application area of plasmas,has attracted much attention of experts from both academic and clinical fields.State-of-the-art of the lab-scale research and clinical trials of the cold atmospheric plasmas(CAPs)in the stomatology are reviewed in detail from the direct and indirect applications of the CAPs.Based on the discussions concerning the relationship between the plasma stomatology and the plasma medicine,it is indicated that it would be an important reference for promoting the TPM starting from the fundamental and application studies in the field of dentistry,which is also one of the most three promising application fields of plasma medicine.展开更多
基金National Natural Science Foundation of China,Grant/Award Number:52177162the Natural Science Foundation of Zhejiang Province,Grant/Award Numbers:LZ22E070003,LQ22E020006+1 种基金the Funding Project for Academic/Technical Leaders of Jiangxi Province,Grant/Award Number:20225BCJ22003the Natural Science Foundation of Jiangxi Province,Grant/Award Number:20212ACB211001。
文摘Engineering high‐performance and low‐cost bifunctional catalysts for H_(2)(hydrogen evolution reaction[HER])and O_(2)(oxygen evolution reaction[OER])evolution under industrial electrocatalytic conditions remains challenging.Here,for the first time,we use the stronger electronegativity of a rare‐Earth yttrium ion(Y^(3+))to induce in situ NiCo‐layered double‐hydroxide nanosheets from NiCo foam(NCF)treated by a dielectric barrier discharge plasma NCF(PNCF),and then obtain nitrogen‐doped YNiCo phosphide(N‐YNiCoP/PNCF)after the phosphating process using radiofrequency plasma in nitrogen.The obtained NYNiCoP/PNCF has a large specific surface area,rich heterointerfaces,and an optimized electronic structure,inducing high electrocatalytic activity in HER(331mV vs.2000mA cm^(−2))and OER(464mV vs.2000mA cm^(−2))reactions in 1MKOH electrolyte.X‐ray absorption spectroscopy and density functional theory quantum chemistry calculations reveal that the coordination number of CoNi decreased with the incorporation of Y atoms,which induce much shorter bonds of Ni and Co ions and promote long‐term stability of N‐YNiCoP in HER and OER under the simulated industrial conditions.Meanwhile,the CoN‐YP_(5)heterointerface formed by plasma N‐doping is the active center for overall water splitting.This work expands the applications of rare‐Earth elements in engineering bifunctional electrocatalysts and provides a new avenue for designing highperformance transition‐metal‐based catalysts in the renewable energy field.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(No.LY23E060004)Royal Society Newton Advanced Fellowship(No.52061130218)
文摘Safe operation of electrochemical capacitors(supercapacitors)is hindered by the flammability of commercial organic electrolytes.Non-flammable Water-in-Salt(WIS)electrolytes are promising alternatives;however,they are plagued by the limited operation voltage window(typically≤2.3 V)and inherent corrosion of current collectors.Herein,a novel deep eutectic solvent(DES)-based electrolyte which uses formamide(FMD)as hydrogen-bond donor and sodium nitrate(NaNO_(3))as hydrogen-bond acceptor is demonstrated.The electrolyte exhibits the wide electrochemical stability window(3.14 V),high electrical conductivity(14.01 mScm^(-1)),good flame-retardance,anticorrosive property,and ultralow cost(7%of the commercial electrolyte and 2%of WIS).Raman spectroscopy and Density Functional Theory calculations reveal that the hydrogen bonds between the FMD molecules and NO_(3)^(-)ions are primarily responsible for the superior stability and conductivity.The developed NaNO_(3)/FMD-based coin cell supercapacitor is among the best-performing state-of-art DES and WIS devices,evidenced by the high voltage window(2.6 V),outstanding energy and power densities(22.77 Wh kg^(-1)at 630 W kg^(-1)and 17.37 kW kg^(-1)at 12.55 Wh kg^(-1)),ultralong cyclic stability(86%after 30000 cycles),and negligible current collector corrosion.The NaNO_(3)/FMD industry adoption potential is demonstrated by fabricating 100 F pouch cell supercapacitors using commercial aluminum current collectors.
基金partially supported by the Australian Research Council(ARC)the National Science Fund for Distinguished Young Scholars(grant number 51925703)。
文摘Sustainable ammonia synthesis at ambient conditions that relies on renewable sources of energy and feedstocks is globally sought to replace the Haber-Bosch process.Here,using nitrogen and water as raw materials,a nonthermal plasma catalysis approach is demonstrated as an effective powerto-chemicals conversion strategy for ammonia production.By sustaining a highly reactive environment,successful plasma-catalytic production of NH_(3) was achieved from the dissociation of N_(2) and H_(2)O under mild conditions.Plasma-induced vibrational excitation is found to decrease the N_(2) and H_(2)O dissociation barriers,with the presence of matched catalysts in the nonthermal plasma discharge reactor contributing significantly to molecular dissociation on the catalyst surface.Density functional theory calculations for the activation energy barrier for the dissociation suggest that ruthenium catalysts supported on magnesium oxide exhibit superior performance over other catalysts in NH_(3) production by lowering the activation energy for the dissociative adsorption of N_(2) down to 1.07 eV.The highest production rate,2.67 mmol gcat.^(-1) h^(-1),was obtained using ruthenium catalyst supported on magnesium oxide.This work highlights the potential of nonthermal plasma catalysis for the activation of renewable sources to serve as a new platform for sustainable ammonia production.
基金supported by the National Natural Science Foundation of China(Grant No.52007023)the Natural Science Foundation of Liaoning Province,China(Grant Nos.2020-BS-073,2019-ZD-0160)+2 种基金the China Postdoctoral Science Foundation(Grant No.2019M661107)the Dalian Maritime University basic scientific research business expenses key scientific research cultivation project(Grant No.3132020371)the Fundamental Research Funds for the Central Universities(Grant No.3132021159).
文摘Surface functionalization or modification to introduce more oxygen-containing functional groups to biochar is an effective strategy for tuning the physicochemical properties and promoting follow-up applications.In this study,non-thermal plasma was applied for biochar surface carving before being used in contaminant removal and energy storage applications.The results showed that even a low dose of plasma exposure could introduce a high number density of oxygen-functional groups and enhance the hydrophilicity and metal affinity of the pristine biochar.The plasma-treated biochar enabled a faster metal-adsorption rate and a 40%higher maximum adsorption capacity of heavy metal ion Pb^(2+).Moreover,to add more functionality to biochar surface,biochar with and without plasma pre-treatment was activated by KOH at a temperature of 800℃.Using the same amount of KOH,the plasma treatment resulted in an activated carbon product with the larger BET surface area and pore volume.The performance of the treated activated carbon as a supercapacitor electrode was also substantially improved by>30%.This study may provide guidelines for enhancing the surface functionality and application performances of biochar using non-thermal-based techniques.
基金National Natural Science Foundation of China,Grant/Award Numbers:52077006,51707012,81801159。
文摘Recent studies have shown the in vitro neuro-protective functions of atmospheric pressure plasma(APP)against multiple pathological injuries during ischaemic stroke(IS).However,whether APP treatment exerts a therapeutic effect on a rat IS model remains unclear.Here,on the basis of needle-to-ring dielectric barrier discharge,an atmospheric pressure plasma jet(APPJ)was designed,with the Helium as the working gas which was driven by a sinusoidal voltage.Then,the treatment conditions were optimised for IS rat model treatment and the characteristics of this APPJ were further diagnosed.Subsequently,the rat IS model was established through 90 min middle cerebral artery occlusion(MCAO),and plasma was intermittently inhaled by rats via the nasal cavity for a 2 min period at 60 min of MCAO process.The therapeutic effects of this plasma jet device were then evaluated using biomedical analyses.According to our results,intermittent APP inhalation in the MCAO rats increased the serum NO content,improved the neurological function,enhanced regional cerebral blood flow,lowered brain infarction,and reduced the cell apoptosis in brain tissues of MCAO rats.Collectively,our data provides a novel potential strategy for IS treatment by using atmospheric-pressure plasma inhalation.
基金supported by the Anhui Provincial Natural Science Foundation(No.2208085MA16)the National Natural Science Foundation of China(No.11575253)+4 种基金the Anhui Provincial key research and development plan(No.1704a0902017)the Anhui Provincial Natural Science Foundation for Distinguished Young Scholars of China(No.1608085J03)the Hefei Institutes of Physical Science,Chinese Academy of Sciences Director’s Fund(No.YZJJ201505)the Key Lab of Photovoltaic and Energy Conservation Materials of Chinese Academy of Sciences(No.PECL2018QN005)K.O.acknowledges partial support from the Australian Research Council(ARC)and QUT Centre for Materials Science.
文摘Methanol oxidation reaction(MOR),the key reaction for clean energy generation in fuel cells,is kinetically sluggish and short-lasting because of insufficient catalytic activity and stability of the common Pt-based electrocatalysts.Ordered Pt alloy structures which promise to surmount these issues,are challenging and impractical to fabricate using common high-temperature annealing.To address the urgent need for simple and rapid synthesis methods for such alloys,here we report the versatile plasma-assisted thermal annealing synthesis of a robust electrocatalyst with PtFe alloys supported on N-doped carbon nanotubes(denoted as PtFe@NCNT-P).Benefiting from the reactive plasma-specific effects,the PtFe@NCNT-P electrocatalyst features ultrafine PtFe alloy nanoparticles(mean size~2.88 nm,ordered degree~87.07%)and ultrathin N-doped carbon(NC)shells(0.3–0.7 nm),leading to the excellent catalytic activity and stability toward MOR.The catalyst shows the specific and mass activities of 3.99 mA/cm^(2)and 2,148.5 mA/mg,which are 7.82 and 7.41 times higher than those for commercial Pt/C(0.51 mA/cm^(2),290 mA/mg),and 2.18 and 2.59 times higher compared to the plasma-untreated PtFe@NCNT(1.83 mA/cm2,829.5 mA/mg),respectively.The PtFe@NCNT-P further exhibits extraordinary stability during the long-term chronoamperometry test and 1,000-cycle cyclic voltammetry scanning,much better compared to PtFe@NCNT samples even after the longer thermal annealing.These findings show great potential of the plasma-enabled synthesis of high-performance carbon-supported metallic electrocatalysts for the emerging clean energy technologies.
文摘Two Minkowski functionals were tested in the capacity of morphological descriptors to quantitatively compare the arrays of vertically-aligned graphene flakes grown on smooth and nanoporous alumina and silica surfaces. Specifically, the Euler-Poincaré characteristic and fractal dimension graphs were used to characterize the degree of connectivity and order in the systems, i.e. in the graphene flake patterns of petal-like and tree-like morphologies on solid substrates, and meshlike patterns (networks) grown on nanoporous alumina treated in low-temperature inductivelycoupled plasma. It was found that the Minkowski functionals return higher connectivity and fractal dimension numbers for the graphene flakepatterns with more complex morphologies, and indeed can be used as morphological descriptors to differentiate among various configurations of vertically-aligned graphene flakes grown on surfaces.
基金National Natural Science Foundation of China(No.52077185)the Basic Research Program of Science and Technology of Shenzhen,China(No.JCYJ20190809162617137)for partial financial support。
文摘A spectrophotometric technique is developed to simultaneously quantify nitrate and nitrite in plasma treated water.The measurement is based on examining the inflection points(wavelengths)in the derivative absorbance of the nitrate or nitrite solution.At the inflection points of the pure nitrate solution,the derivative absorbance is zero and independent of the nitrate’s concentration,and thus the nitrite’s concentration in a mixed nitrate and nitrite solution can be obtained by using the Beer’s law at these points.The nitrate’s concentration can also be achieved from the inflection points of nitrite in the same manner.The relation between the tested substance’s(nitrate or nitrite)concentration and the second-or the third-order absorbances is obtained at these inflection points.Test measurements for mixed aqueous solutions of nitrate and nitrite with or without hydrogen peroxide confirm the reliability of this technique.We applied this technique to quantify the nitrate and nitrite generated in air plasma treated aqueous solutions.The results indicate that both nitrate and nitrite concentrations increase with the plasma treatment time,and the nitrite species is found to be generated prior to the nitrate species in the air plasma treated aqueous solution.Moreover,the production rate of total nitrogen species is independent of the solutions’p H value.These results are relevant to diverse applications of plasma activated solutions in materials processing,biotechnology,medicine and other fields.
基金Australian Research Council,Grant/Award Numbers:FL170100154,FT200100062,DP220102596,DP210100472,DP190103472。
文摘Converting CO_(2) into high‐value fuels and chemicals by renewable‐electricitypowered electrochemical CO_(2) reduction reaction(CRR)is a viable approach toward carbon‐emissions‐neutral processes.Unlike the thermocatalytic hydrogenation of CO_(2) at the solid‐gas interface,the CRR takes place at the three‐phase gas/solid/liquid interface near the electrode surface in aqueous solution,which leads to major challenges including the limited mass diffusion of CO_(2) reactant,competitive hydrogen evolution reaction,and poor product selectivity.Here we critically examine the various methods of surface and interface engineering of the electrocatalysts to optimize the microenvironment for CRR,which can address the above issues.The effective modification strategies for the gas transport,electrolyte composition,controlling intermediate states,and catalyst engineering are discussed.The key emphasis is made on the diverse atomic‐precision modifications to increase the local CO_(2) concentration,lower the energy barriers for CO_(2) activation,decrease the H2O coverage,and stabilize intermediates to effectively control the catalytic activity and selectivity.The perspectives on the challenges and outlook for the future applications of three‐phase interface engineering for CRR and other gasinvolving electrocatalytic reactions conclude the article.
基金Basic Research Program of Science and Technology of Shenzhen,China,Grant/Award Number:JCYJ20190809162617137Australian Research Council(ARC)+1 种基金National Natural Science Foundation of China,Grant/Award Number:52077185QUT Centre for Materials Science。
文摘The aqueous phase hydrogen peroxide(H_(2)O_(2aq))produced from the plasma-liquid interactions can directly or synergistically(with other substances)affect the liquid chemistry,and therefore it is important to unfold the H_(2)O_(2aq)formation mechanism.However,up to now,a consensus on the H_(2)O_(2aq)formation mechanism is not reached.This review aims to survey the recent advances on the understanding of the H_(2)O_(2aq)formation mechanism in the system of a direct current discharge plasma operated over a liquid electrode.Theoretical and experimental analyses indicate that the recombination of dissolved OH radicals(OHaq)is the dominant process for the H_(2)O_(2aq)formation,while the purported plasma-induced photolysis of water and the dissolution of gaseous H_(2)O_(2)are ruled out.
基金supported by the National Natural Science Foundation of China(22005273,21825106,and 21671175)the Program for Science&Technology Innovative Research Team in the University of Henan Province(20IRTSTHN007)the Australian Research Council and QUT Centre for Materials Science for partial support。
文摘Heterostructure engineering holds exceptional promise for the development of high-performance electrocatalysts for overall water splitting.However,production of inexpensive and high-efficiency bifunctional electrocatalysts remains a challenge.Herein,we demonstrate a simple method to synthesize a paper-mulberry(Broussonetia papyrifera)-inspired Co_(9)S_(8)@CoNi_(2)S_(4)/nickel foam(Co_(9)S_(8)@CoNi_(2)S_(4)/NF)heterojunction with high catalytic activity and stability.The process involves in situ growth of NiCo layered double hydroxide and in situ derivatization of ZIF-67,followed by the S heteroatom doping.The Co_(9)S_(8)@CoNi_(2)S_(4)/NF benefits from the heterostructure and functional advantages of multidimensional building blocks including one-dimensional(1D)nanowires,2D nanosheets and nanoparticles.The optimized Co_(9)S_(8)@CoNi_(2)S_(4)/NF heterojunction with 10% sulphur content reveals excellent electrocatalytic activity with the lower overpotentials of 68 mV for hydrogen evolution reaction(HER)and 170 mV for oxygen evolution reaction(OER)at 10 mA cm^(-2) in the 1.0 mol L^(-1) KOH solution,which is superior to the recently reported transition metal based electrocatalysts.The outstanding performance is attributed to the strong interface coupling between CoNi_(2)S_(4) and Co_(9)S_(8),the advantage of multidimensional structure and the customized electronic structure.The density functional theory suggests that the interface between Co_(9)S_(8) and CoNi_(2)S_(4) optimizes the adsorption of the multiple intermediates and further facilitates water splitting kinetics.This work offers a generic approach for heterostructure engineering design of highperformance catalytic system applications.
基金the Basic Research Program of Science and Technology of Shenzhen, China (No. JCYJ20190809162617137)National Natural Science Foundation of China (No. 52077185) for partial financial support+1 种基金the Australian Research Council (ARC)QUT Center for Materials Science for partial support
文摘Dual argon plasmas ignited by one direct current power source are used to treat an aqueous solution of hydrogen tetrachloroaurate-(Ⅲ)trihydrate(HAuCl_(4)·3H_(2)O)which is contained in an H-type electrochemical cell.The solution contained in one cell acts as a cathode,and in the other as an anode.Experiments are carried out to directly visualize the formation process of gold nanoparticles(Au NPs)in separated cells of the H-type electrochemical reactor.The results and analyzes suggest that hydrogen peroxide and hydrated electrons generated from the plasma-liquid interactions play the roles of reductants in the solutions,respectively.Hydrogen peroxide can be generated in the case of the liquid being a cathode or an anode,while most of hydrated electrons are formed in the case of the liquid being an anode.Therefore,the reduction of the AuCl_(4)−ions is mostly attributed to the hydrogen peroxide as the liquid acts as a cathode,while to the hydrogen peroxide and hydrated electrons as the liquid acts as an anode.Moreover,the p H value of the solution can be used to tune the formation processes and final form of the Au NPs due to its mediation of reductants.
基金supported by National Natural Science Foundation of China(Nos.51907088,51677019)。
文摘In this work,a portable floating-electrode dielectric barrier discharge(FE-DBD)device is designed with a rechargeable battery as the power supply.The characteristics of the FE-DBD with a metal electrode and human hand are studied and compared.The human contact safety is verified by calculating the current through the human body based on the equivalent circuit model.Escherichia coli inactivation experiments confirm the efficacy of the FE-DBD device in the envisaged applications.
基金This work was supported by the Foundation of Key Laboratory of Biomass Chemical Engineering of Ministry of Education,China(Zhejiang University,No.2018BCE006)We are also grateful to the Australian Research Council for their partial support.
文摘Non-thermal plasma exhibits unique advan-tages in biomass conversion for the sustainable production of higher-value energy carriers.Different homogeneous catalysts are usually required for plasma-enabled biomass liquefaction to achieve time-and energy-efficient conver-sions.However,the effects of such catalysts on the plasma-assisted liquefaction process and of the plasma on those catalysts have not been thoroughly studied.In this study,an electrical discharge plasma is employed to promote the direct liquefaction of sawdust in a mixture of polyethylene glycol 200 and glycerol.Three commonly used chemicals,sulfuric acid,nitric acid and sodium p-toluene sulfate,were selected as catalysts.The effects of the type of catalyst and concentration on the liquefaction yield were examined;further,the roles of the catalysts in the plasma liquefaction process have been discussed.The results showed that the liquefaction yield attains a value of 90%within 5 min when 1%sulfuric acid was employed as the catalyst.Compared with the other catalysts,sulfuric acid presents the highest efficiency for the liquefaction of sawdust.It was observed that hydrogen ions from the catalyst were primarily responsible for the significant thermal effects on the liquefaction system and the generation of large quantities of active species;these effects directly con-tributed to a higher efficacy of the plasma-enabled liquefaction process.
基金National Natural Science Foundation of China(No.52077185)the Basic Research Program of Science and Technology of Shenzhen,China(No.JCYJ20190809162617137)for partial financial support+6 种基金the financial supports from the Basic Ability Promotion Project for Young and Middle-Aged Teachers in Universities of Guangxi(No.2018KY0083)Doctoral Scientific Research Fund of Guangxi Normal University(No.2017BQ019)the financial supports from National Natural Science Foundation of China(No.11975061)the Technology Innovation and Application Development Project of Chongqing(No.cstc2019jscxmsxm X0041)the Construction Committee Project of Chongqing(No.2018-1-3-6)the Fundamental Research Funds for the Central Universities(No.2019CDQYDQ034)the Australian Research Council(ARC)for partial support。
文摘The quantification of hydrogen peroxide(H_(2)O_(2))generated in the plasma-liquid interactions is of great importance,since the H_(2)O_(2)species is vital for the applications of the plasma-liquid system.Herein,we report on in situ quantification of the aqueous H_(2)O_(2)(H_(2)O_(2)aq)using a colorimetric method for the DC plasma-liquid systems with liquid as either a cathode or an anode.The results show that the H_(2)O_(2)aqyield is 8-12 times larger when the liquid acts as a cathode than when the liquid acts as an anode.The conversion rate of the gaseous OH radicals to H_(2)O_(2)aqis 4-6 times greater in the former case.However,the concentrations of dissolved OH radicals for both liquid as cathode and anode are of the same order of tens of n M.
基金support from the Zhejiang Provincial Natural Science Foundation of China(No.LR23C160001)the National Key Research and Development Program of China(No.2021YFD2100504).
文摘Cellulose macrofibers (MFs) are gaining increasing interest as natural and biodegradable alternatives to fossil-derived polymers for both structural and functional applications. However, simultaneously achieving their exceptional mechanical performance and desired functionality is challenging and requires complex processing. Here, we reported a one-step approach using a tension-assisted twisting (TAT) technique for MF fabrication from bacterial cellulose (BC). The TAT stretches and aligns BC nanofibers pre-arranged in hydrogel tubes to form MFs with compactly assembled structures and enhanced hydrogen bonding among neighboring nanofibers. The as-prepared BC MFs exhibited a very high tensile strength of 1 057 MPa and exceptional lifting capacity (over 340 000 when normalized by their own weight). Moreover, due to the volume expansion of BC nanofibers upon water exposure, BC MFs quickly harvested energy from environmental moisture to untwist the bundled networks, thus generating a torsional spinning with a peak rotation speed of 884 r/(min·m). The demonstrated rapid and intense actuation response makes the MFs ideal candidates for diverse humidity-response-based applications beyond advanced actuators, remote rain indicators, intelligent switches, and smart curtains.
基金support from the National Key R&D Program of China(2020YFD0900900)Science and Technology Planning Project of Zhoushan of China(2022C41001)Zhejiang Ocean University(11135091221)。
文摘Low-value,renewable,carbon-rich resources,with different biomass feedstocks and their derivatives as typical examples,represent virtually inexhaustive carbon sources and carbon-related energy on Earth.Upon conversion to higher-value forms(referred to as“up-carbonization”here),these abundant feedstocks provide viable opportunities for energy-rich fuels and sustainable platform chemicals production.However,many of the current methods for such up-carbonization still lack sufficient energy,cost,and material efficiency,which affect their economics and carbon-emissions footprint.With external electricity precisely delivered,discharge plasmas enable many stubborn reactions to occur under mild conditions,by creating locally intensified and highly reactive environments.This technology emerges as a novel,versatile technology platform for integrated or stand-alone conversion of carbon-rich resources.The plasma-based processes are compatible for integration with increasingly abundant and cost-effective renewable electricity,making the whole conversion carbon-neutral and further paving the plasma-electrified upcarbonization to be performance-,environment-,and economics-viable.Despite the chief interest in this emerging area,no review article brings together the state-of-the-art results from diverse disciplines and underlies basic mechanisms and chemistry underpinned.As such,this review aims to fill this gap and provide basic guidelines for future research and transformation,by providing an overview of the application of plasma techniques for carbon-rich resource conversion,with particular focus on the perspective of discharge plasmas,the fundamentals of why plasmas are particularly suited for upcarbonization,and featured examples of plasma-enabled resource valorization.With parallels drawn and specificity highlighted,we also discuss the technique shortcomings,current challenges,and research needs for future work.
基金the National Natural Science Foundation of China(nos.51707012 and 11475019).
文摘Plasma is an ionized gas.It is typically formed at high temperature.As a result of both the development of bow-temperature plasma sources and a better understanding of complex plasma phenomena over the last decade,"plasma medicine"has become a booming interdisciplinary research topic of growing importance that explores enormous opportunities at the interface of chemistry,plasma physics,and biomedical sciences with engineering.This review presents the latest development in plasma medicine in the area of the central nervous system and aims to introduce cutting-edge plasma medicine to clinical and translational medical researchers and practitioners.
基金supported by the National Natural Science Foundation of China(grant no.11475103)the Natural Science Foundation of Beijing(grant no.7162204).
文摘In recent years,translational plasma medicine(TPM),as a novel application area of plasmas,has attracted much attention of experts from both academic and clinical fields.State-of-the-art of the lab-scale research and clinical trials of the cold atmospheric plasmas(CAPs)in the stomatology are reviewed in detail from the direct and indirect applications of the CAPs.Based on the discussions concerning the relationship between the plasma stomatology and the plasma medicine,it is indicated that it would be an important reference for promoting the TPM starting from the fundamental and application studies in the field of dentistry,which is also one of the most three promising application fields of plasma medicine.
