The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces c...The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.展开更多
Plasma-assisted ball milling was carried out on the Al+C3H6N6 system and Al+C_(4)H_(4)N_(4) system,respectively.The phase structure,functional groups and synthesis mechanism were analyzed by XRD and FT-IR,and the diff...Plasma-assisted ball milling was carried out on the Al+C3H6N6 system and Al+C_(4)H_(4)N_(4) system,respectively.The phase structure,functional groups and synthesis mechanism were analyzed by XRD and FT-IR,and the differences in the synthesis process of nano-AlN with different solid nitrogen sources were discussed.The results show that C3H6N6 has a stable triazine ring structure,and its chemical bond is firm and difficult to break,so AlN cannot be synthesized directly by solid-solid reaction at room temperature.However,there are a large number of nitrile groups(-CN)and amino groups(-NH_(2))in C_(4)H_(4)N_(4) molecules.Under the combined action of plasma bombardment and mechanical energy activation,C_(4)H_(4)N_(4) molecules undergo polycondensation and deamination,so that the ball milling tank is filled with a large number of active nitrogen-containing groups such as N=,≡N,etc.These groups and ball milling activated Al can synthesize nano-AlN at room temperature,with a conversion rate of 92%.SEM,DSC/TG analysis showed that the powder obtained by ball milling was formed by soft agglomeration of many fine primary particles about 50–80 nm.The surface morphology of the powder was loose and porous,and it had strong activity.After annealing at 800℃,the conversion rate of the Al+C_(4)H_(4)N_(4) system reached 99%.展开更多
Metal aluminum (A1) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the ...Metal aluminum (A1) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited A1 films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.展开更多
A two-dimensional mathematical model was developed to investigate the effects of dielectric barrier discharge (DBD) plasma on CH4-air mixtures combustion at atmospheric pressure. Considering the physical and chemica...A two-dimensional mathematical model was developed to investigate the effects of dielectric barrier discharge (DBD) plasma on CH4-air mixtures combustion at atmospheric pressure. Considering the physical and chemical processes of plasma-assisted combustion (PAC), plasma discharge, heat transfer and turbulent were simultaneously coupled into simulation of PAC. This coupling model consists of DBD kinetic model and methane combustion model. By comparing simulations and the original reference's results, a high-accuracy of this model was validated. In addition, the effects of PAC actuation parameters on combustion characteristics were studied. Numerical simulations show that with an inlet airflow velocity of 10 m s-1, a CH4-air mixtures' equivalence ratio of 0.5, an applied voltage of 10 kV, a frequency of 1200 kHz, compared to conventional combustion (CC), the highest flame temperature rises by 32 K; outlet temperature distribution coefficient drops by 2.3%; the maximum net reaction rate of CH4 and H20 increase by 11.22% and 12.80% respectively; the maximum CO emission index decreases by 14.61%; the mixing region turbulence mixing time reduces by 89 ms.展开更多
The effects of the airflow on plasma-assisted combustion actuator (PACA) characteristics are studied in detail. The plasma is characterized electrically, as well as optically with a spectrometer. Our results show th...The effects of the airflow on plasma-assisted combustion actuator (PACA) characteristics are studied in detail. The plasma is characterized electrically, as well as optically with a spectrometer. Our results show that the airflow has an obvious influence on the PACA characteristics. The breakdown voltage and vibrational temperature decrease, while the discharge power increases compared with the stationary airflow. The memory effect of metastable state species and the transportation characteristics of charged particles in microdischarge channel are the dominant causes for the variations of the breakdown voltage and discharge power, respectively, and the vibrational temperature calculated in this work can describe the electron energy of the dielectric barrier discharge plasma in PACA. These results offer new perspectives for the use of PACA in plasma-assisted combustion.展开更多
Pollution involving pharmaceutical components in bodies of water is an increasingly serious environmental issue.Plasma discharge for the degradation of antibiotics is an emerging technology that may be relevant toward...Pollution involving pharmaceutical components in bodies of water is an increasingly serious environmental issue.Plasma discharge for the degradation of antibiotics is an emerging technology that may be relevant toward addressing this issue.In this work,a plasma-assisted rotating disk reactor(plasma-RDR)and a photocatalyst—namely,titanium dioxide(TiO_(2))—were coupled for the treatment of metronidazole(MNZ).Discharge uniformity was improved by the use of a rotating electrode in the plasma-RDR,which contributed to the utilization of ultraviolet(UV)light radiation in the presence of TiO_(2).The experimental results showed that the degradation efficiency of MNZ and the concentration of generated hydroxyl radicals respectively increased by 41%and 2.954 mg∙L^(-1) as the rotational speed increased from 0 to 500 r∙min^(-1).The synergistic effect of plasma-RDR plus TiO_(2) on the generation of hydroxyl radicals was evaluated.Major intermediate products were identified using three-dimensional(3D)excitation emission fluorescence matrices(EEFMs)and liquid chromatography-mass spectrometry(LC-MS),and a possible degradation pathway is proposed herein.This plasma-catalytic process has bright prospects in the field of antibiotics degradation.展开更多
In this paper, the effects of thickness of AlN nucleation layer grown at high temperature on AlN epi-layer crystalline quality are investigated. Crack-ftee AlN samples with various nucleation thicknesses are grown on ...In this paper, the effects of thickness of AlN nucleation layer grown at high temperature on AlN epi-layer crystalline quality are investigated. Crack-ftee AlN samples with various nucleation thicknesses are grown on sapphire substrates by plasma-assisted molecular beam epitaxy. The AlN crystalline quality is analysed by transmission electron microscope and x-ray diffraction (XRD) rocking curves in both (002) and (102) planes. The surface profiles of nucleation layer with different thicknesses after in-situ annealing are also analysed by atomic force microscope. A critical nucleation thickness for realising high quality AlN films is found. When the nucleation thickness is above a certain value, the (102) XRD full width at half maximum (FWHM) of AlN bulk increases with nucleation thickness increasing, whereas the (002) XRD FWHM shows an opposite trend. These phenomena can be attributed to the characteristics of nucleation islands and the evolution of crystal grains during AlN main layer growth.展开更多
The authors report that the growth rate of ZnO can be significantly increased by modifying the oxygen plasma conditions in plasma-assisted molecular beam epitaxy. Both the aperture diameter and the distance between th...The authors report that the growth rate of ZnO can be significantly increased by modifying the oxygen plasma conditions in plasma-assisted molecular beam epitaxy. Both the aperture diameter and the distance between the plasma source and the substrate affect the growth rate and the quality of the ZnO films. A short source to substrate distance is essential in achieving higher growth rate, which is explained by reduced chance of oxygen atom collisions to accommodate the short oxygen mean free path at high background pressure. At a shorter source to substrate distance, the growth rate is higher with a larger aperture diameter. The quality of the ZnO thin films grown under different conditions is assessed by x-ray diffraction and room-temperature photoluminescence measurements.展开更多
Mutual effects between a gliding arc(GA)discharge at atmospheric pressure and a premixed CH_(4)/air flame were experimentally investigated.Effects of the flame on the GA were studied using simultaneous measurements of...Mutual effects between a gliding arc(GA)discharge at atmospheric pressure and a premixed CH_(4)/air flame were experimentally investigated.Effects of the flame on the GA were studied using simultaneous measurements of the current,the voltage,and the instantaneous images of the plasma columns.The GA in the flame has a thicker and more diffusive plasma column,and it is more frequently ignited at a smaller breakdown voltage than that in the air.The GA extension velocity and the gliding velocity in the flame are larger than those in the air.The electrode voltage drop of the GA discharge in the flame is about 160 V,whereas that in the air is about 220 V.Compared with the GA in the air,the different features of the GA in the flame can be explained by high-temperature,weakly ionized,and species-abundant environment that are generated by the premixed CH_(4)/air flame.Effects of the gliding arc discharge on the premixed flames were demonstrated using planar laser-induced fluorescence of hydroxyl radicals(OH)and formaldehyde(CH_(2)O).OH and CH_(2)O can be formed in the CH_(4)/air mixture in the presence of the GA due to kinetic effects,and the increase of OH and CH_(2)O shows the great potential of the GA for combustion enhancement.展开更多
To optimize the design of plasma injectors,the influence of different external electrodes on plasma-assisted flame stabilization was assessed by using a nonequilibrium plasma injector flame control setup.The electrica...To optimize the design of plasma injectors,the influence of different external electrodes on plasma-assisted flame stabilization was assessed by using a nonequilibrium plasma injector flame control setup.The electrical characteristics of the injector,flame structure parameters,flame intensity,discharge power,and cost-to-effectiveness ratio under different external electrodes(four mesh electrodes and one copper foil electrode)were analyzed using electrical and optical methods.The results show that reducing the mesh size of the external electrode leads to a decrease in breakdown voltage.Compared with a ceramic dielectric barrier-based injector,an injector with a quartz dielectric barrier produces a higher breakdown voltage under the same conditions.For the same actuation voltage,the discharge current increases as the mesh size of the external electrode decreases,and combustion is enhanced by the discharge plasma;therefore,it is better to adopt a smaller mesh hole size to realize good flame stabilization under a lower actuation voltage.However,under the studied working conditions,reducing the mesh hole size of the external electrode increases the cost-to-effectiveness ratio of plasma injector-based flame stabilization.Thus,considering the cost-to-effectiveness ratio and the weight of the injector,an external electrode with a larger mesh hole size should be chosen,which contradicts the above rule.展开更多
The activation and reduction of N_(2)to produce ammonia under mild conditions is of great interest,but challenges remain.Here,we report a breakthrough in efficient dinitrogen cleavage by employing small Ptn+(n=1–4)cl...The activation and reduction of N_(2)to produce ammonia under mild conditions is of great interest,but challenges remain.Here,we report a breakthrough in efficient dinitrogen cleavage by employing small Ptn+(n=1–4)clusters and convenient plasma assistance.The reactivity of Pt3+is found to be substantially higher than that of other clusters,and the formed Pt3N7+shows prominent mass abundance among the odd-nitrogen products.We illustrate that a chain reaction path within dual cluster cooperation,especially via a“3+2”mode,is beneficial to N≡N triple bond dissociation,embodying efficient synergistic catalysis.A key intermediate containing a bridged N_(2)of binding with two Pt clusters facilitates N_(2)activation with significantly enhanced interactions between the d orbitals of Pt and the antibondingπ*-orbitals of N_(2).Furthermore,by reacting the Pt_(n)N_(m)+clusters with H_(2),we observed hydrogenation products of both evenand odd-hydrogen species,indicative of ammonia release.The in situ synthesized platinum nitride clusters,typically Pt_(3)N_(7)+,induce a highly active N site for hydrogen anchoring,enabling a cost-effective hydrotreating process for ammonia synthesis.展开更多
Polycrystalline tin is an ideal excitation material for extreme ultraviolet light sources.However,the existence of grain boundary(GB)limits the surface roughness of polycrystalline tin after single-point diamond turni...Polycrystalline tin is an ideal excitation material for extreme ultraviolet light sources.However,the existence of grain boundary(GB)limits the surface roughness of polycrystalline tin after single-point diamond turning(SPDT).In this work,a novel method termed inductively coupled plasma(ICP)-assisted cutting was developed for the sub-nanometer finishing of polycrystalline tin.The relationship between ICP power,processing time,and modification depth was established by thermodynamic simulation,and the fitted heat transfer coefficient of polycrystalline tin was 540 W/(m2·K).The effects of large-thermal-gradient ICP treatment on the microstructure of polycrystalline tin were studied.After 0.9 kW ICP processing for 3.0 s,corresponding to the temperature gradient of 0.30 K/μm,the grain size of polycrystalline tin was expanded from a size of approximately 20-80μm to a millimeter scale.The Taguchi method was used to investigate the effects of rotational speed,depth of cut,and feed rate on SPDT.Experiments conducted based on the ICP system indicated that the plasma-assisted cutting method promoted the reduction of the influence of GB steps on the finishing of polycrystalline tin,thereby achieving a surface finish from 8.53 to 0.80 nm in Sa.The results of residual stress release demonstrated that the residual stress of plasma-assisted turning processing after 504 h stress release was 10.7 MPa,while that of the turning process without the ICP treatment was 41.6 MPa.展开更多
基金partial support from the Jiujiang Research Institute at Xiamen University.
文摘The electrochemical carbon dioxide reduction(eCO_(2)RR)to formate,driven by clean energy,is a promising approach for producing renewable chemicals and high-value fuels.Despite its potential,further development faces challenges due to limitations in electrocatalytic activity and durability,especially for nonnoble metal-based catalysts.Here,naturally abundant bismuth-based nanosheets that can effectively drive CO_(2)-to-formate electrocatalytic reduction are prepared using the plasma-activated Bi_(2)Se_(3) followed by a reduction process.Thus-obtained plasma-activated Bi nanosheets(P-BiNS)feature ultrathin structures and high surface areas.Such nanostructures ensure the P-BiNS with outstanding eCO_(2)RR catalytic performance,highlighted by the current density of over 80 mA cm^(-2) and a formate Faradic efficiency of>90%.Furthermore,P-BiNS catalysts demonstrate excellent durability and stability without deactivation following over 50h of operation.The selectivity for formate production is also studied by density functional theory(DFT)calculations,validating the importance and efficacy of the stabilization of intermediates(^(*)OCHO)on the P-BiNS surfaces.This study provides a facile plasma-assisted approach for developing high-performance and low-cost electrocatalysts.
基金The study was supported by the Education and Research Project for Young and Middle-Aged Teachers in Fujian Province(JAT201167).
文摘Plasma-assisted ball milling was carried out on the Al+C3H6N6 system and Al+C_(4)H_(4)N_(4) system,respectively.The phase structure,functional groups and synthesis mechanism were analyzed by XRD and FT-IR,and the differences in the synthesis process of nano-AlN with different solid nitrogen sources were discussed.The results show that C3H6N6 has a stable triazine ring structure,and its chemical bond is firm and difficult to break,so AlN cannot be synthesized directly by solid-solid reaction at room temperature.However,there are a large number of nitrile groups(-CN)and amino groups(-NH_(2))in C_(4)H_(4)N_(4) molecules.Under the combined action of plasma bombardment and mechanical energy activation,C_(4)H_(4)N_(4) molecules undergo polycondensation and deamination,so that the ball milling tank is filled with a large number of active nitrogen-containing groups such as N=,≡N,etc.These groups and ball milling activated Al can synthesize nano-AlN at room temperature,with a conversion rate of 92%.SEM,DSC/TG analysis showed that the powder obtained by ball milling was formed by soft agglomeration of many fine primary particles about 50–80 nm.The surface morphology of the powder was loose and porous,and it had strong activity.After annealing at 800℃,the conversion rate of the Al+C_(4)H_(4)N_(4) system reached 99%.
基金Project supported by the National Natural Science Foundation of China (Grant No. 11175024)the Beijing Natural Science Foundation, China (Grant No. 1112012)+1 种基金the Science and Technology on Surface Engineering Laboratorythe Beijing Education Committee, China (Grant Nos. BM201002, 2011BAD24B01, KM201110015008, KM201010015005, and PHR20110516)
文摘Metal aluminum (A1) thin films are prepared by 2450 MHz electron cyclotron resonance plasma-assisted atomic layer deposition on glass and p-Si substrates using trimethylaluminum as the precursor and hydrogen as the reductive gas. We focus our attention on the plasma source for the thin-film preparation and annealing of the as-deposited films relative to the surface square resistivity. The square resistivity of as-deposited A1 films is greatly reduced after annealing and almost reaches the value of bulk metal. Through chemical and structural analysis, we conclude that the square resistivity is determined by neither the contaminant concentration nor the surface morphology, but by both the crystallinity and crystal size in this process.
基金supported by National Natural Science Foundation of China(No.51436008)
文摘A two-dimensional mathematical model was developed to investigate the effects of dielectric barrier discharge (DBD) plasma on CH4-air mixtures combustion at atmospheric pressure. Considering the physical and chemical processes of plasma-assisted combustion (PAC), plasma discharge, heat transfer and turbulent were simultaneously coupled into simulation of PAC. This coupling model consists of DBD kinetic model and methane combustion model. By comparing simulations and the original reference's results, a high-accuracy of this model was validated. In addition, the effects of PAC actuation parameters on combustion characteristics were studied. Numerical simulations show that with an inlet airflow velocity of 10 m s-1, a CH4-air mixtures' equivalence ratio of 0.5, an applied voltage of 10 kV, a frequency of 1200 kHz, compared to conventional combustion (CC), the highest flame temperature rises by 32 K; outlet temperature distribution coefficient drops by 2.3%; the maximum net reaction rate of CH4 and H20 increase by 11.22% and 12.80% respectively; the maximum CO emission index decreases by 14.61%; the mixing region turbulence mixing time reduces by 89 ms.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.51436008,50776100,and 51106179)
文摘The effects of the airflow on plasma-assisted combustion actuator (PACA) characteristics are studied in detail. The plasma is characterized electrically, as well as optically with a spectrometer. Our results show that the airflow has an obvious influence on the PACA characteristics. The breakdown voltage and vibrational temperature decrease, while the discharge power increases compared with the stationary airflow. The memory effect of metastable state species and the transportation characteristics of charged particles in microdischarge channel are the dominant causes for the variations of the breakdown voltage and discharge power, respectively, and the vibrational temperature calculated in this work can describe the electron energy of the dielectric barrier discharge plasma in PACA. These results offer new perspectives for the use of PACA in plasma-assisted combustion.
基金This work was supported by the National Natural Science Foundation of China(21725601).
文摘Pollution involving pharmaceutical components in bodies of water is an increasingly serious environmental issue.Plasma discharge for the degradation of antibiotics is an emerging technology that may be relevant toward addressing this issue.In this work,a plasma-assisted rotating disk reactor(plasma-RDR)and a photocatalyst—namely,titanium dioxide(TiO_(2))—were coupled for the treatment of metronidazole(MNZ).Discharge uniformity was improved by the use of a rotating electrode in the plasma-RDR,which contributed to the utilization of ultraviolet(UV)light radiation in the presence of TiO_(2).The experimental results showed that the degradation efficiency of MNZ and the concentration of generated hydroxyl radicals respectively increased by 41%and 2.954 mg∙L^(-1) as the rotational speed increased from 0 to 500 r∙min^(-1).The synergistic effect of plasma-RDR plus TiO_(2) on the generation of hydroxyl radicals was evaluated.Major intermediate products were identified using three-dimensional(3D)excitation emission fluorescence matrices(EEFMs)and liquid chromatography-mass spectrometry(LC-MS),and a possible degradation pathway is proposed herein.This plasma-catalytic process has bright prospects in the field of antibiotics degradation.
基金Project supported by the National Natural Science Foundation of China (Grant Nos. 60536020 and 60723002)the National Basic Research Program of China (Grant Nos. 2006CB302800 and 2006CB921106)+1 种基金the National High Technology Research and Development Program for Advanced Materials of China (Grant No. 2006AA03A105)the Major Project of Beijing Municipal Science and Technology Commission,China (Grant No. D0404003040321)
文摘In this paper, the effects of thickness of AlN nucleation layer grown at high temperature on AlN epi-layer crystalline quality are investigated. Crack-ftee AlN samples with various nucleation thicknesses are grown on sapphire substrates by plasma-assisted molecular beam epitaxy. The AlN crystalline quality is analysed by transmission electron microscope and x-ray diffraction (XRD) rocking curves in both (002) and (102) planes. The surface profiles of nucleation layer with different thicknesses after in-situ annealing are also analysed by atomic force microscope. A critical nucleation thickness for realising high quality AlN films is found. When the nucleation thickness is above a certain value, the (102) XRD full width at half maximum (FWHM) of AlN bulk increases with nucleation thickness increasing, whereas the (002) XRD FWHM shows an opposite trend. These phenomena can be attributed to the characteristics of nucleation islands and the evolution of crystal grains during AlN main layer growth.
文摘The authors report that the growth rate of ZnO can be significantly increased by modifying the oxygen plasma conditions in plasma-assisted molecular beam epitaxy. Both the aperture diameter and the distance between the plasma source and the substrate affect the growth rate and the quality of the ZnO films. A short source to substrate distance is essential in achieving higher growth rate, which is explained by reduced chance of oxygen atom collisions to accommodate the short oxygen mean free path at high background pressure. At a shorter source to substrate distance, the growth rate is higher with a larger aperture diameter. The quality of the ZnO thin films grown under different conditions is assessed by x-ray diffraction and room-temperature photoluminescence measurements.
基金financially supported by National Natural Science Foundation of China(Nos.12172379,12322211,and 11925207)。
文摘Mutual effects between a gliding arc(GA)discharge at atmospheric pressure and a premixed CH_(4)/air flame were experimentally investigated.Effects of the flame on the GA were studied using simultaneous measurements of the current,the voltage,and the instantaneous images of the plasma columns.The GA in the flame has a thicker and more diffusive plasma column,and it is more frequently ignited at a smaller breakdown voltage than that in the air.The GA extension velocity and the gliding velocity in the flame are larger than those in the air.The electrode voltage drop of the GA discharge in the flame is about 160 V,whereas that in the air is about 220 V.Compared with the GA in the air,the different features of the GA in the flame can be explained by high-temperature,weakly ionized,and species-abundant environment that are generated by the premixed CH_(4)/air flame.Effects of the gliding arc discharge on the premixed flames were demonstrated using planar laser-induced fluorescence of hydroxyl radicals(OH)and formaldehyde(CH_(2)O).OH and CH_(2)O can be formed in the CH_(4)/air mixture in the presence of the GA due to kinetic effects,and the increase of OH and CH_(2)O shows the great potential of the GA for combustion enhancement.
基金supported by Beijing Natural Science Foundation(No.3222062)National Natural Science Foundation of China(No.12102482)。
文摘To optimize the design of plasma injectors,the influence of different external electrodes on plasma-assisted flame stabilization was assessed by using a nonequilibrium plasma injector flame control setup.The electrical characteristics of the injector,flame structure parameters,flame intensity,discharge power,and cost-to-effectiveness ratio under different external electrodes(four mesh electrodes and one copper foil electrode)were analyzed using electrical and optical methods.The results show that reducing the mesh size of the external electrode leads to a decrease in breakdown voltage.Compared with a ceramic dielectric barrier-based injector,an injector with a quartz dielectric barrier produces a higher breakdown voltage under the same conditions.For the same actuation voltage,the discharge current increases as the mesh size of the external electrode decreases,and combustion is enhanced by the discharge plasma;therefore,it is better to adopt a smaller mesh hole size to realize good flame stabilization under a lower actuation voltage.However,under the studied working conditions,reducing the mesh hole size of the external electrode increases the cost-to-effectiveness ratio of plasma injector-based flame stabilization.Thus,considering the cost-to-effectiveness ratio and the weight of the injector,an external electrode with a larger mesh hole size should be chosen,which contradicts the above rule.
基金This work was financially supported by the National Natural Science Foundation of China(grant nos.21802146 and 21722308)the CAS Key Research Project of Frontier Science(CAS grant no.QYZDB-SSW-SLH024)the Frontier Cross Project of national laboratory for molecular sciences(grant no.051Z011BZ3).
文摘The activation and reduction of N_(2)to produce ammonia under mild conditions is of great interest,but challenges remain.Here,we report a breakthrough in efficient dinitrogen cleavage by employing small Ptn+(n=1–4)clusters and convenient plasma assistance.The reactivity of Pt3+is found to be substantially higher than that of other clusters,and the formed Pt3N7+shows prominent mass abundance among the odd-nitrogen products.We illustrate that a chain reaction path within dual cluster cooperation,especially via a“3+2”mode,is beneficial to N≡N triple bond dissociation,embodying efficient synergistic catalysis.A key intermediate containing a bridged N_(2)of binding with two Pt clusters facilitates N_(2)activation with significantly enhanced interactions between the d orbitals of Pt and the antibondingπ*-orbitals of N_(2).Furthermore,by reacting the Pt_(n)N_(m)+clusters with H_(2),we observed hydrogenation products of both evenand odd-hydrogen species,indicative of ammonia release.The in situ synthesized platinum nitride clusters,typically Pt_(3)N_(7)+,induce a highly active N site for hydrogen anchoring,enabling a cost-effective hydrotreating process for ammonia synthesis.
基金financial support from the National Natural Science Foundation of China(Grant No.52035009)the Science Challenge Project,China(Grant No.TZ2018006-0201-01)+1 种基金the National Key R&D Program of China(Grant No.2016YFB1102203)the“111”project by the State Administration of Foreign Experts Affairs and the Ministry of Education of China(Grant No.B07014).
文摘Polycrystalline tin is an ideal excitation material for extreme ultraviolet light sources.However,the existence of grain boundary(GB)limits the surface roughness of polycrystalline tin after single-point diamond turning(SPDT).In this work,a novel method termed inductively coupled plasma(ICP)-assisted cutting was developed for the sub-nanometer finishing of polycrystalline tin.The relationship between ICP power,processing time,and modification depth was established by thermodynamic simulation,and the fitted heat transfer coefficient of polycrystalline tin was 540 W/(m2·K).The effects of large-thermal-gradient ICP treatment on the microstructure of polycrystalline tin were studied.After 0.9 kW ICP processing for 3.0 s,corresponding to the temperature gradient of 0.30 K/μm,the grain size of polycrystalline tin was expanded from a size of approximately 20-80μm to a millimeter scale.The Taguchi method was used to investigate the effects of rotational speed,depth of cut,and feed rate on SPDT.Experiments conducted based on the ICP system indicated that the plasma-assisted cutting method promoted the reduction of the influence of GB steps on the finishing of polycrystalline tin,thereby achieving a surface finish from 8.53 to 0.80 nm in Sa.The results of residual stress release demonstrated that the residual stress of plasma-assisted turning processing after 504 h stress release was 10.7 MPa,while that of the turning process without the ICP treatment was 41.6 MPa.