Understanding the degradation phenomenon of proton exchange membrane fuel cells under electrochemical cycling requires an analysis of the porous carbon support structure.Key factors contributing to this phenomenon inc...Understanding the degradation phenomenon of proton exchange membrane fuel cells under electrochemical cycling requires an analysis of the porous carbon support structure.Key factors contributing to this phenomenon include changes in the total porosity and viable surface area for electrochemical reactions.Electron tomography-based serial section imaging using focused ion beam-scanning electron microscopy(FIB-SEM)can elucidate this phenomenon at a nanoscale resolution.However,this highresolution tomographic analysis requires a huge image dataset and manual inputs in rule-based workflows;these requirements are time-consuming and often cause experimental difficulties and unreliable interpretations.We propose a deep learning-empowered approach comprising a two-step automated process for image interpolation and semantic segmentation to address the practical issues encountered in FIB-SEM electron tomography.An optimally trained interpolation model can reduce the image data requirement by more than 95%to analyze the structural degradation of carbon supports after electrochemical cycling while maintaining the reliability obtained in conventional tomographic analysis with several hundred images.Because the subsequent image segmentation model excludes a complicated manual filtering process,the relevant structural parameters can be reliably measured without human bias.Our sparse-section imaging-based deep learning process can allow cost-efficient analysis and reliable measurement of the degree of cycling-induced carbon corrosion.展开更多
Combinations of graphene(Gr)and carbon black(C)were employed as binary carbon supports to fabricate Pd‐based electrocatalysts via one‐pot co‐reduction with Pd2+.The electrocatalytic performance of the resulting Pd...Combinations of graphene(Gr)and carbon black(C)were employed as binary carbon supports to fabricate Pd‐based electrocatalysts via one‐pot co‐reduction with Pd2+.The electrocatalytic performance of the resulting Pd/Gr‐C catalysts during the electrooxidation of formic acid was assessed.A Pd/Gr0.3C0.7(Gr oxide:C=3:7,based on the precursor mass ratio)electrocatalyst exhibited better catalytic performance than both Pd/C and Pd/Gr catalysts.The current density generated by the Pd/Gr0.3C0.7catalyst was as high as102.14mA mgPd?1,a value that is approximately3times that obtained from the Pd/C(34.40mA mgPd?1)and2.6times that of the Pd/Gr material(38.50mA mgPd?1).The anodic peak potential of the Pd/Gr0.3C0.7was120mV more negative than that of the Pd/C and70mV more negative than that of the Pd/Gr.Scanning electron microscopy images indicated that the spherical C particles accumulated on the wrinkled graphene surfaces to form C cluster/Gr hybrids having three‐dimensional nanostructures.X‐ray photoelectron spectroscopy data confirmed the interaction between the Pd metal and the binary Gr‐C support.The Pd/Gr0.3C0.7also exhibited high stability,and so is a promising candidate for the fabrication of anodes for direct formic acid fuel cells.This work demonstrates a simple and cost‐effective method for improving the performance of Pd‐based electrocatalysts,which should have potential industrial applications.展开更多
Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carb...Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carbon supports. XPS and IR-spectroscopy data show the formation of rhodium chalcogen halides in solids prepared by different methods. We have found that the productivity of acetic acid by carbon supported rhodium chalcogen halides depends strongly on the carbon carrier and the method of the catalyst preparation. Namely, the catalyst with highest productivity for the acetic acid is prepared by synthesizing the rhodium chalcogen halide over the carbon support followed by thermal destruction. We have also found that rhodium chalcogen halides over activated carbons are more active compared with fullerene supported catalysts.展开更多
Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct intera...Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.展开更多
Developing platinum-group-metal(PGM)catalysts possessing strong metal-support interaction and controllable PGM size is urgent for the sluggish oxygen reduction reaction(ORR)in proton-exchange membrane fuel cells.Herei...Developing platinum-group-metal(PGM)catalysts possessing strong metal-support interaction and controllable PGM size is urgent for the sluggish oxygen reduction reaction(ORR)in proton-exchange membrane fuel cells.Herein,we propose an in-situ self-assembled reduction strategy to successfully induce highly-dispersed sub-3nm platinum nanoparticles(Pt NPs)to attach on resin-derived atomic Co coordinated by N-doped carbon substrate(Pt/Co_(SA)-N-C)for ORR.To be specific,the interfacial electron interaction effect,along with a highly robust Co_(SA)-N-C support endow the as-fabricated Pt/Co_(SA)-N-C catalyst with significantly enhanced catalytic properties,i.e.,a mass activity(MA)of 0.719 A/mgPt at 0.9 ViR-free and a reduction of 24.2%in MA after a 20,000-cycles test.Density functional theory(DFT)calculations demonstrate that the enhanced electron interaction between Pt and Co_(SA)-N-C support decreases the dband center of Pt,which is in favor of lowering the desorption energy of ^(*)OH on Pt/Co_(SA)-N-C surface and accelerating the formation of H_(2)O,thus enhance the instinct activity of ORR.Furthermore,the higher binding energy between Pt and Co_(SA)-N-C compared to Pt and C indicates that the migration of Pt has been suppressed,which theoretically explains the improved durability of Pt/Co_(SA)-N-C.Our work offers an enlightenment on constructing composite Pt-based catalysts with multiple active sites.展开更多
A supported Mn-porphyrin catalyst was prepared by adsorption of Mn-porphyrin on active carbon, and found to be efficient for the hydroxylation of hexane with hydrogen peroxide.
Colloidal synthesis method such as oleylamine(OAm)-stabilized process is of great interest for obtaining uniform and highly dispersed platinum nanoparticle catalysts, yet the ligand may unavoidably inhibit their elect...Colloidal synthesis method such as oleylamine(OAm)-stabilized process is of great interest for obtaining uniform and highly dispersed platinum nanoparticle catalysts, yet the ligand may unavoidably inhibit their electro-catalytic performance. Thus, fully removing these ligands is critical to activate catalyst surface. Previous research of OAm removal process pointed that thermal annealing was the most effective way in comparison with other methods such as chemical washing, UV–Ozone irradiation and cyclic voltammetry sweeping, but generally resulting in undesired growth of platinum nanoparticle. Few studies concerning a more efficient ligand removal process have been published yet. In this work we proposed a platinum in-situ catalytic OAm combustion strategy to elucidate the removal mechanism of OAm ligands in thermal process and the key experimental parameters were also optimized. In addition, heat flow signal based on differential scanning calorimetry(DSC) measurement as a sensitive indicator, is suggested to reveal the ligand removal efficiency, which is much more reliable than the traditional spectroscopy.In comparison with commercial Pt/C sample, such a surface clean Pt/C electrocatalyst has shown an enhanced specific activity for oxygen reduction reaction. Our removal strategy and the evaluation method are highly instructive to efficient removal of different organic ligands.展开更多
A series of high surface area graphitic carbon materials （HSGCs） were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x （x is the ball-milling t...A series of high surface area graphitic carbon materials （HSGCs） were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x （x is the ball-milling time in hour） catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.展开更多
The carbon supported PtRu alloy film electrodes having Pt about 0.10 mg/cm2 or even less were prepared by ion beam sputtering method （IBSM）. It was valued on the hydrogen analyse performance, the temperature influen...The carbon supported PtRu alloy film electrodes having Pt about 0.10 mg/cm2 or even less were prepared by ion beam sputtering method （IBSM）. It was valued on the hydrogen analyse performance, the temperature influence factor and the stability by electroanalysis hydrogen analyse method. It was found that the carbon supported PtRu alloy film electrodes had higher hydrogen evolution performance and stability, such as the hydrogen evolution exchange current density （j0） was increase as the temperature （T） rised, and it overrun 150 mA/cm2 as the trough voltage in about 0.68V, and it only had about 2.8% decline in 500 h electrolytic process. The results demonstrated that the carbon supported PtRu alloy film electrodes kept highly catalytic activity and stability, and it were successfully used in pilot plant for producing H2 on electrolysis of H2S.展开更多
Mesoporous carbon supports mitigate platinum(Pt)sulfonic poisoning through nanopore-confined Pt deposition,yet their morphological impacts on oxygen transport remain unclear.This study integrates carbon support morpho...Mesoporous carbon supports mitigate platinum(Pt)sulfonic poisoning through nanopore-confined Pt deposition,yet their morphological impacts on oxygen transport remain unclear.This study integrates carbon support morphology simulation with an enhanced agglomerate model to establish a mathematical framework elucidating pore evolution,Pt utilization,and oxygen transport in catalyst layers.Results demonstrate dominant local mass transport resistance governed by three factors:(1)active site density dictating oxygen flux;(2)ionomer film thickness defining shortest transport path;(3)ionomer-to-Pt surface area ratio modulating practical pathway length.At low ionomer-to-carbon(I/C)ratios,limited active sites elevate resistance(Factor 1 dominant).Higher I/C ratios improve the ionomer coverage but eventually thicken ionomer films,degrading transport(Factors 2–3 dominant).The results indicate that larger carbon particles result in a net increase in local transport resistance by reducing external surface area and increasing ionomer thickness.As the proportion of Pt situated in nanopores or the Pt mass fraction increases,elevated Pt density inside the nanopores exacerbates pore blockage.This leads to the increased transport resistance by reducing active sites,and increasing ionomer thickness and surface area.Lower Pt loading linearly intensifies oxygen flux resistance.The model underscores the necessity to optimize support morphology,Pt distribution,and ionomer content to prevent pore blockage while balancing catalytic activity and transport efficiency.These insights provide a systematic approach for designing high-performance mesoporous carbon catalysts.展开更多
The widespread commercial adoption of fuel cells requires continued improvements in cost-effectiveness,performance,and durability.A tree-like nitrogen-doped carbon(T-NC)support structure was developed for low-platinum...The widespread commercial adoption of fuel cells requires continued improvements in cost-effectiveness,performance,and durability.A tree-like nitrogen-doped carbon(T-NC)support structure was developed for low-platinum(Pt)loaded fuel cells.Carbon nanotubes serve as the conductive backbone,while ZIF-8-derived carbon,synthesized from 2-methylimidazole zinc salt,forms the branches that provide attachment sites for platinum group metals(PGMs).In cathodes with a Pt loading of 0.1 mgPt/cm^(2),this novel Pt/T-NC electrode exhibited a remarkable 30%reduction in concentration loss at 2.0 A/cm^(2) and a 12.7%increase in peak power density,compared to conventional Pt/C electrodes.Additionally,the corrosion resistance of the electrode was improved.Following 5000 cycles of accelerated durability testing(ADT)for carbon corrosion,the fuel cell retained 50.8%of its original performance,while conventional electrodes retained only 38%.The T-NC structure is broadly applicable for supporting various advanced PGM catalysts.This advancement offers a promising approach to bridge the gap between theoretical catalytic activity and practical output,leading to substantial improvements in both performance and durability of fuel cells.展开更多
Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,...Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.展开更多
The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The ca...The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.展开更多
Carbon materials were used as supports for Ag catalysts that are prepared using the conventional wet impregnation method, and their catalytic properties for CO selective oxidation in excess hydrogen at temperatures be...Carbon materials were used as supports for Ag catalysts that are prepared using the conventional wet impregnation method, and their catalytic properties for CO selective oxidation in excess hydrogen at temperatures below 483 K were tested. A variety of techniques, e.g. N2 adsorption, XPS, TPD, UV-Vis DRS, TEM and SEM, were used to determine the influence of physical and chemical properties of the carbon on the properties of Ag catalyst. It was found that defects on the carbon surface served as nucleation sites for silver ions, while functional groups on carbon surface induced their reduction to the metallic form. The formation of silver particles on carbon was governed by homogeneous and/or heterogeneous nucleation during the impregnation and subsequent activation processes. The best catalytic performance was obtained with a Ag/carbon black catalyst with a uniform size distribution of silver nanoparticles （about 12 nm）, moderate BET surface area （with a mesoporous structure）, and a limited amount of carbon-oxygen groups. The research indicates that carbon materials are potentially good supports for silver catalysts for preferential oxidation of CO in excess hydrogen.展开更多
Activation of(bi)sulfite(S(IV))by metal oxides is strongly limited by low electrons utilization.In this study,two carbon-supported cobalt ferrites spinels(CoFe^(2)O_(4) QDs-GO and CoFe^(2)O_(4) MOFs-CNTs)have been suc...Activation of(bi)sulfite(S(IV))by metal oxides is strongly limited by low electrons utilization.In this study,two carbon-supported cobalt ferrites spinels(CoFe^(2)O_(4) QDs-GO and CoFe^(2)O_(4) MOFs-CNTs)have been successfully synthesized by one-step solvothermal method.It was found that both catalysts could efficiently activate S(IV),with rapid reductive dechlorination and then oxidative degradation of a recalcitrant antibiotic chloramphenicol(CAP).Characterizations revealed that CoFe^(2)O_(4) spinels were tightly coated on the carbon bases(GO and CNTs),with effectiveness of the internal transfer of electrons.O_(2)˙−was identified for the reductive dechlorination of CAP,with simultaneously detection of both•OH and SO_(4)^(˙−)responsible for further oxidative degradation.The sulfur oxygen radical conversion reactions and molecular oxygen activation would occur together upon the carbon-based spinels.Spatial-separated interfacial reductive-oxidation of CAP would occur with dechlorination of CAP by O_(2)^(˙−)on the carbon bases,and oxidative degradation of intermediates by SO_(4)^(˙−/•)OH upon the CoFe^(2)O_(4) catalysts.展开更多
The activated carbon-supported TiO2 nanoparticles(TiO2/AC)were prepared by a properly controlled sol-gel method.The effects of activated carbons(AC)support on inactivated properties of TiO2 nanoparticles were evaluate...The activated carbon-supported TiO2 nanoparticles(TiO2/AC)were prepared by a properly controlled sol-gel method.The effects of activated carbons(AC)support on inactivated properties of TiO2 nanoparticles were evaluated by photocatalytic inactivation experiments of Escherichia coli.The key factors affecting the inactivation effciency were investigated,including electric power of lamp, temperature,and pH values.The results show that the TiO2/AC composites have high inactivation properties of E.coli in compari...展开更多
TiO2 sol was prepared by sol-gel technique with tetrabutyl titanate as precursor. Supported TiO2 catalysts on activated carbon were prepared by soak and sintering method. The aggregation of nano-TiO2 particles can be ...TiO2 sol was prepared by sol-gel technique with tetrabutyl titanate as precursor. Supported TiO2 catalysts on activated carbon were prepared by soak and sintering method. The aggregation of nano-TiO2 particles can be effectively suppressed by added polyethylene glycol （PEG） as a surface modifier. The average particle diameter of TiO2, specific surface area and absorbability of catalyst can be modified. Based on characteristics of the TiO2 photocatalyst with XRD, specific surface area, adsorption valves of methylene blue and the amount of TiO2 supported on the activated carbon, the photocatalytic degradation of L-acid was studied. The effect of the factors, such as pH of the solution, the initial concentration of L-acid on the photocatalytic degradation of L-acid, were studied also. It was found that when the pH of the solution is 1.95, the amount of photocatalyst is 0.5 g, the concentration of the L-acid solution is 1.34×10^3 mol/L and the illumination time is 7 h, the photocatalytic degradation efficiency of L-acid can reach 89,88%, The catalyst was reused 6 times and its degradation efficiency hardly changed.展开更多
Ten kinds of activated carbon from different raw materials were used as supports to prepare ruthenium catalysts. N_2 physisorption and CO chemisorption were carried out to investigate the pore size distribution and th...Ten kinds of activated carbon from different raw materials were used as supports to prepare ruthenium catalysts. N_2 physisorption and CO chemisorption were carried out to investigate the pore size distribution and the ruthenium dispersion of the catalysts. It was found that the Ru dispersion of the catalyst was closely related to not only the texture of carbon support but also the purity of activated carbon. The activities of a series of the carbon-supported barium-promoted Ru catalysts for ammonia synthesis were measured at 425 ℃, 10 0 MPa and 10 000 h -1. The result shows that the same raw material activated carbon, with a high purity, high surface area, large pore volume and reasonable pore size distribution might disperse ruthenium and promoter sufficiently, which activated carbon as support, could be used to manufacture ruthenium catalyst with a high activity for ammonia synthesis. The different raw material activated carbon as the support would greatly influence the catalytic properties of the ruthenium catalyst for ammonia synthesis. For example, with coconut shell carbon(AC1) as the support, the ammonia concentration in the effluent was 13 17% over 4%Ru-BaO/AC1 catalyst, while with the desulfurized coal carbon(AC10) as the support, that in the effluent was only 1 37% over 4%Ru-BaO/AC10 catalyst.展开更多
A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on t...A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.展开更多
Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and wer...Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and were identified to be Cu（0） and Cu（Ⅰ） in XRD patterns. Excellent catalytic activity and selectivity were achieved in the N-arylation of pyrazole under ligand and protection gas free conditions. About90.4% of product yield was achieved with only 0.5 mol% of copper catalyst（Cu-C-300）, which was considerably more efficient than previous reports. XPS results suggested that the N-arylation of pyrazole activity was closely related to the surface Cu（Ⅰ） species.展开更多
基金supported by the Technology Innovation Program(No.20011712)funded by the Ministry of Trade,Industry,and Energy(MOTIE,Korea)a National Research Foundation of Korea(NRF)grant funded by the Ministry of Science and ICT(MSIT)(No.2022M3J1A108538),Korea+2 种基金the support of the Nano&Material Technology Development Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Science and ICT(RS-2024-00444986,50%)the Institute for Basic Science(IBS-R036-D1)。
文摘Understanding the degradation phenomenon of proton exchange membrane fuel cells under electrochemical cycling requires an analysis of the porous carbon support structure.Key factors contributing to this phenomenon include changes in the total porosity and viable surface area for electrochemical reactions.Electron tomography-based serial section imaging using focused ion beam-scanning electron microscopy(FIB-SEM)can elucidate this phenomenon at a nanoscale resolution.However,this highresolution tomographic analysis requires a huge image dataset and manual inputs in rule-based workflows;these requirements are time-consuming and often cause experimental difficulties and unreliable interpretations.We propose a deep learning-empowered approach comprising a two-step automated process for image interpolation and semantic segmentation to address the practical issues encountered in FIB-SEM electron tomography.An optimally trained interpolation model can reduce the image data requirement by more than 95%to analyze the structural degradation of carbon supports after electrochemical cycling while maintaining the reliability obtained in conventional tomographic analysis with several hundred images.Because the subsequent image segmentation model excludes a complicated manual filtering process,the relevant structural parameters can be reliably measured without human bias.Our sparse-section imaging-based deep learning process can allow cost-efficient analysis and reliable measurement of the degree of cycling-induced carbon corrosion.
基金supported by the Natural Science Foundation of Shandong Province(ZR2016BM31)the Science and Technology Foundation of Jinan City(201311035)~~
文摘Combinations of graphene(Gr)and carbon black(C)were employed as binary carbon supports to fabricate Pd‐based electrocatalysts via one‐pot co‐reduction with Pd2+.The electrocatalytic performance of the resulting Pd/Gr‐C catalysts during the electrooxidation of formic acid was assessed.A Pd/Gr0.3C0.7(Gr oxide:C=3:7,based on the precursor mass ratio)electrocatalyst exhibited better catalytic performance than both Pd/C and Pd/Gr catalysts.The current density generated by the Pd/Gr0.3C0.7catalyst was as high as102.14mA mgPd?1,a value that is approximately3times that obtained from the Pd/C(34.40mA mgPd?1)and2.6times that of the Pd/Gr material(38.50mA mgPd?1).The anodic peak potential of the Pd/Gr0.3C0.7was120mV more negative than that of the Pd/C and70mV more negative than that of the Pd/Gr.Scanning electron microscopy images indicated that the spherical C particles accumulated on the wrinkled graphene surfaces to form C cluster/Gr hybrids having three‐dimensional nanostructures.X‐ray photoelectron spectroscopy data confirmed the interaction between the Pd metal and the binary Gr‐C support.The Pd/Gr0.3C0.7also exhibited high stability,and so is a promising candidate for the fabrication of anodes for direct formic acid fuel cells.This work demonstrates a simple and cost‐effective method for improving the performance of Pd‐based electrocatalysts,which should have potential industrial applications.
文摘Gas phase carbonylation of methane is studied in the presence of molecular oxygen over pure carbon carriers and carbon supported rhodium chalcogen halides. Activated carbons and fullerene blacks have been used as carbon supports. XPS and IR-spectroscopy data show the formation of rhodium chalcogen halides in solids prepared by different methods. We have found that the productivity of acetic acid by carbon supported rhodium chalcogen halides depends strongly on the carbon carrier and the method of the catalyst preparation. Namely, the catalyst with highest productivity for the acetic acid is prepared by synthesizing the rhodium chalcogen halide over the carbon support followed by thermal destruction. We have also found that rhodium chalcogen halides over activated carbons are more active compared with fullerene supported catalysts.
基金supported by the Natural Science Foundation of Beijing Municipality (Z200012)the National Natural Science Foundation of China (U21A20328,22225903)the National Key Research and Development Program of China (2021YFB4000601)。
文摘Metal nanoaggregates can simultaneously enhance the activity and stability of Fe-N-C catalysts in proton-exchange-membrane fuel cells(PEMFC).Previous studies on the relevant mechanism have focused on the direct interaction between FeN_(4)active sites and metal nanoaggregates.However,the role of carbon support that hosts metal nanoaggregates and active sites has been overlooked.Here,a Fe-N-C catalyst encapsulating inactive gold nanoparticles is prepared as a model catalyst to investigate the electronic tuning of Au nanoparticles(NPs)towards the carbon support.Au NPs donate electrons to carbon support,making it rich inπelectrons,which reduces the work function and regulates the electronic configuration of the FeN_(4)sites for an enhanced ORR activity.Meanwhile,the electron-rich carbon support can mitigate the electron depletion of FeN_(4)sites caused by carbon support oxidation,thereby preserving its high activity.The yield and accumulation of H_(2)O_(2)are thus alleviated,which delays the oxidation of the catalyst and benefits the stability.Due to the electron-rich carbon support,the composite catalyst achieves a top-level peak power density of 0.74 W/cm^(2) in a 1.5 bar H_(2)-air PEMFC,as well as the improved stability.This work elucidates the key role of carbon support in the performance enhancement of the FeN-C/metal nanoaggregate composite catalysts for fuel cell application.
基金financially supported by the Natural Science Foundation of China(Nos.22169005,22209186,22068009 and 22262006)the Science and Technology Support Project of Guizhou Provincial Science and Technology Department(Nos.ZK[2023]050 and[2023]403)+2 种基金the Open Project of Institute of Dualcarbon and New Energy Technology Innovation and Development of Guizhou Province(No.DCRE-2023-06)Youth Innovation Promotion Association,CAS(No.2023343)Self-deployed Projects of Ganjiang Innovation Academy,CAS(No.E355F006).
文摘Developing platinum-group-metal(PGM)catalysts possessing strong metal-support interaction and controllable PGM size is urgent for the sluggish oxygen reduction reaction(ORR)in proton-exchange membrane fuel cells.Herein,we propose an in-situ self-assembled reduction strategy to successfully induce highly-dispersed sub-3nm platinum nanoparticles(Pt NPs)to attach on resin-derived atomic Co coordinated by N-doped carbon substrate(Pt/Co_(SA)-N-C)for ORR.To be specific,the interfacial electron interaction effect,along with a highly robust Co_(SA)-N-C support endow the as-fabricated Pt/Co_(SA)-N-C catalyst with significantly enhanced catalytic properties,i.e.,a mass activity(MA)of 0.719 A/mgPt at 0.9 ViR-free and a reduction of 24.2%in MA after a 20,000-cycles test.Density functional theory(DFT)calculations demonstrate that the enhanced electron interaction between Pt and Co_(SA)-N-C support decreases the dband center of Pt,which is in favor of lowering the desorption energy of ^(*)OH on Pt/Co_(SA)-N-C surface and accelerating the formation of H_(2)O,thus enhance the instinct activity of ORR.Furthermore,the higher binding energy between Pt and Co_(SA)-N-C compared to Pt and C indicates that the migration of Pt has been suppressed,which theoretically explains the improved durability of Pt/Co_(SA)-N-C.Our work offers an enlightenment on constructing composite Pt-based catalysts with multiple active sites.
文摘A supported Mn-porphyrin catalyst was prepared by adsorption of Mn-porphyrin on active carbon, and found to be efficient for the hydroxylation of hexane with hydrogen peroxide.
基金the financial support by DICP Grant no.ZZBS201705。
文摘Colloidal synthesis method such as oleylamine(OAm)-stabilized process is of great interest for obtaining uniform and highly dispersed platinum nanoparticle catalysts, yet the ligand may unavoidably inhibit their electro-catalytic performance. Thus, fully removing these ligands is critical to activate catalyst surface. Previous research of OAm removal process pointed that thermal annealing was the most effective way in comparison with other methods such as chemical washing, UV–Ozone irradiation and cyclic voltammetry sweeping, but generally resulting in undesired growth of platinum nanoparticle. Few studies concerning a more efficient ligand removal process have been published yet. In this work we proposed a platinum in-situ catalytic OAm combustion strategy to elucidate the removal mechanism of OAm ligands in thermal process and the key experimental parameters were also optimized. In addition, heat flow signal based on differential scanning calorimetry(DSC) measurement as a sensitive indicator, is suggested to reveal the ligand removal efficiency, which is much more reliable than the traditional spectroscopy.In comparison with commercial Pt/C sample, such a surface clean Pt/C electrocatalyst has shown an enhanced specific activity for oxygen reduction reaction. Our removal strategy and the evaluation method are highly instructive to efficient removal of different organic ligands.
基金supported by the Natural Science Foundation of China(NSFC Grant No.20803064)the Natural Science Foundation of Zhejiang Provence(Y4090348 and LY12B03007)Qianjiang Talent Project in Zhejiang Province(2010R10039 and 2013R10056)
文摘A series of high surface area graphitic carbon materials （HSGCs） were prepared by ball-milling method. Effect of the graphitic degree of HSGCs on the catalytic performance of Ba-Ru-K/HSGC-x （x is the ball-milling time in hour） catalysts was studied using ammonia synthesis as a probe reaction. The graphitic degree and pore structure of HSGC-x supports could be successfully tuned via the variation of ball-milling time. Ru nanoparticles of different Ba-Ru-K/HSGC-x catalysts are homogeneously distributed on the supports with the particle sizes ranging from 1.6 to 2.0 nm. The graphitic degree of the support is closely related to its facile electron transfer capability and so plays an important role in improving the intrinsic catalytic performance of Ba-Ru-K/HSGC-x catalyst.
文摘The carbon supported PtRu alloy film electrodes having Pt about 0.10 mg/cm2 or even less were prepared by ion beam sputtering method （IBSM）. It was valued on the hydrogen analyse performance, the temperature influence factor and the stability by electroanalysis hydrogen analyse method. It was found that the carbon supported PtRu alloy film electrodes had higher hydrogen evolution performance and stability, such as the hydrogen evolution exchange current density （j0） was increase as the temperature （T） rised, and it overrun 150 mA/cm2 as the trough voltage in about 0.68V, and it only had about 2.8% decline in 500 h electrolytic process. The results demonstrated that the carbon supported PtRu alloy film electrodes kept highly catalytic activity and stability, and it were successfully used in pilot plant for producing H2 on electrolysis of H2S.
基金supported by the Program of Ministry of Science and Technology of China(No.2023YFB2504200)support of Shanghai Rising-Star Program(Grant No.24QB2703200)the Major Science and Technology Projects of Yunnan Province(No.202302AH360001).
文摘Mesoporous carbon supports mitigate platinum(Pt)sulfonic poisoning through nanopore-confined Pt deposition,yet their morphological impacts on oxygen transport remain unclear.This study integrates carbon support morphology simulation with an enhanced agglomerate model to establish a mathematical framework elucidating pore evolution,Pt utilization,and oxygen transport in catalyst layers.Results demonstrate dominant local mass transport resistance governed by three factors:(1)active site density dictating oxygen flux;(2)ionomer film thickness defining shortest transport path;(3)ionomer-to-Pt surface area ratio modulating practical pathway length.At low ionomer-to-carbon(I/C)ratios,limited active sites elevate resistance(Factor 1 dominant).Higher I/C ratios improve the ionomer coverage but eventually thicken ionomer films,degrading transport(Factors 2–3 dominant).The results indicate that larger carbon particles result in a net increase in local transport resistance by reducing external surface area and increasing ionomer thickness.As the proportion of Pt situated in nanopores or the Pt mass fraction increases,elevated Pt density inside the nanopores exacerbates pore blockage.This leads to the increased transport resistance by reducing active sites,and increasing ionomer thickness and surface area.Lower Pt loading linearly intensifies oxygen flux resistance.The model underscores the necessity to optimize support morphology,Pt distribution,and ionomer content to prevent pore blockage while balancing catalytic activity and transport efficiency.These insights provide a systematic approach for designing high-performance mesoporous carbon catalysts.
基金supported by the National Natural Science Foundation of China for Distinguished Young Scholars(Grant No.52225604)Jilin Province Science and Technology Development Program,China(Grant No.20230301017ZD).
文摘The widespread commercial adoption of fuel cells requires continued improvements in cost-effectiveness,performance,and durability.A tree-like nitrogen-doped carbon(T-NC)support structure was developed for low-platinum(Pt)loaded fuel cells.Carbon nanotubes serve as the conductive backbone,while ZIF-8-derived carbon,synthesized from 2-methylimidazole zinc salt,forms the branches that provide attachment sites for platinum group metals(PGMs).In cathodes with a Pt loading of 0.1 mgPt/cm^(2),this novel Pt/T-NC electrode exhibited a remarkable 30%reduction in concentration loss at 2.0 A/cm^(2) and a 12.7%increase in peak power density,compared to conventional Pt/C electrodes.Additionally,the corrosion resistance of the electrode was improved.Following 5000 cycles of accelerated durability testing(ADT)for carbon corrosion,the fuel cell retained 50.8%of its original performance,while conventional electrodes retained only 38%.The T-NC structure is broadly applicable for supporting various advanced PGM catalysts.This advancement offers a promising approach to bridge the gap between theoretical catalytic activity and practical output,leading to substantial improvements in both performance and durability of fuel cells.
基金China Postdoctoral Science Foundation (2023M733451)Dalian Innovation Team in Key Areas(2020RT06)Engineering Research Center for Key Aromatic Compounds and LiaoNing Key Laboratory,Liaoning Provincial Natural Science Foundation (Doctoral Research Start-up Fund 2024-BSBA-37)。
文摘Selective hydrogenation of furfural to furfuryl alcohol is a great challenge in the hydrogenation field due to thermodynamic preference for hydrogenation of C=C over C=O.Herein,a novel Al_(2)O_(3)/C-u hybrid catalyst,composed of N-modified dendritic carbon networks supporting Al_(2)O_(3)nanoparticles,was successfully prepared via carbonizing the freeze-dried gel from spontaneous cross-linking of alginate,Al3+and urea.The obtained carbon-supported Al_(2)O_(3)hybrid catalyst has a high ratio (31%) of Al species in pentahedral-coordinated state.The introduction of urea enhances the surface N content,the ratio of pyrrolic N,and specific surface area of catalyst,leading to improved adsorption capacity of C=O and the accessibility of active sites.In the furfural hydrogenation reaction with isopropyl alcohol as hydrogen donor,Al_(2)O_(3)/C-u catalyst achieved a 90%conversion of furfural with 98.0% selectivity to furfuryl alcohol,outperforming that of commercial γ-Al_(2)O_(3).Moreover,Al_(2)O_(3)/C-u demonstrates excellent catalytic stability in the recycling tests attributed to the synergistic effect of abundant weak Lewis acid sites and the anchoring effect of the carbon network on Al_(2)O_(3)nanoparticles.This work provides an innovative and facile strategy for fabrication of carbon-supported Al_(2)O_(3)hybrid catalysts with rich AlVspecies,serving as a high selective hydrogenation catalyst through MPV reaction route.
基金supported by a Post Doc grant of the German Academic Exchange Service(Deutscher Akademischer Austauschdienst,DAAD grant no.91552012)by the European Research Council(EU FP7 ERC advanced grant no.338846)
文摘The Fischer–Tropsch to olefins（FTO） process is a method for the direct conversion of synthesis gas to lower C–Colefins. Carbon-supported iron carbide nanoparticles are attractive catalysts for this reaction.The catalytic activity can be improved and undesired formation of alkanes can be suppressed by the addition of sodium and sulfur as promoters but the influence of their content and ratio remains poorly understood and the promoted catalysts often suffer from rapid deactivation due to particle growth. A series of carbon black-supported iron catalysts with similar iron content and nominal sodium/sulfur loadings of 1–30/0.5–5 wt% with respect to iron are prepared and characterized under FTO conditions at 1and 10 bar syngas pressure to illuminate the influence of the promoter level on the catalytic properties.Iron particles and promoters undergo significant reorganization during FTO operation under industrially relevant conditions. Low sodium content（1–3 wt%） leads to a delay in iron carbide formation. Sodium contents of 15–30 wt% lead to rapid loss of catalytic activity due to the covering of the iron surface with promoters during particle growth under FTO operation. Higher activity and slower loss of activity are observed at low promoter contents（1–3 wt% sodium and 0.5–1 wt% sulfur） but a minimum amount of alkali is required to effectively suppress methane and C–Cparaffin formation. A reference catalyst support（carbide-derived carbon aerogel） shows that the optimum promoter level depends on iron particle size and support pore structure.
基金the Chinese Ministry of Science and Technology (2003CB6 15806) the Natural Science Foundation of China (National Key Project: 90206036).
文摘Carbon materials were used as supports for Ag catalysts that are prepared using the conventional wet impregnation method, and their catalytic properties for CO selective oxidation in excess hydrogen at temperatures below 483 K were tested. A variety of techniques, e.g. N2 adsorption, XPS, TPD, UV-Vis DRS, TEM and SEM, were used to determine the influence of physical and chemical properties of the carbon on the properties of Ag catalyst. It was found that defects on the carbon surface served as nucleation sites for silver ions, while functional groups on carbon surface induced their reduction to the metallic form. The formation of silver particles on carbon was governed by homogeneous and/or heterogeneous nucleation during the impregnation and subsequent activation processes. The best catalytic performance was obtained with a Ag/carbon black catalyst with a uniform size distribution of silver nanoparticles （about 12 nm）, moderate BET surface area （with a mesoporous structure）, and a limited amount of carbon-oxygen groups. The research indicates that carbon materials are potentially good supports for silver catalysts for preferential oxidation of CO in excess hydrogen.
基金financially-supported by the National Natural Science Foundation of China(Nos.21677055,22006045 and 21407052)the National Key Technical Research and Development Program of China(No.2019YFC1805204)+1 种基金Leading Plan for Scientific and Technological Innovation of High-tech Industries of Hunan Province(No.2021GK4060)the Fundamental Research Funds for the Central Universities,HUST(No.2017KFXKJC004).
文摘Activation of(bi)sulfite(S(IV))by metal oxides is strongly limited by low electrons utilization.In this study,two carbon-supported cobalt ferrites spinels(CoFe^(2)O_(4) QDs-GO and CoFe^(2)O_(4) MOFs-CNTs)have been successfully synthesized by one-step solvothermal method.It was found that both catalysts could efficiently activate S(IV),with rapid reductive dechlorination and then oxidative degradation of a recalcitrant antibiotic chloramphenicol(CAP).Characterizations revealed that CoFe^(2)O_(4) spinels were tightly coated on the carbon bases(GO and CNTs),with effectiveness of the internal transfer of electrons.O_(2)˙−was identified for the reductive dechlorination of CAP,with simultaneously detection of both•OH and SO_(4)^(˙−)responsible for further oxidative degradation.The sulfur oxygen radical conversion reactions and molecular oxygen activation would occur together upon the carbon-based spinels.Spatial-separated interfacial reductive-oxidation of CAP would occur with dechlorination of CAP by O_(2)^(˙−)on the carbon bases,and oxidative degradation of intermediates by SO_(4)^(˙−/•)OH upon the CoFe^(2)O_(4) catalysts.
基金supported by the Educational and Tech-nological Department of Hunan Province(No.08B063)the Natural Science Foundation of Science and Technology Department of Hunan Government(No.2007GK3060)the Doctor Foundation of Jishou University(No.JSDXKYZZ200648).
文摘The activated carbon-supported TiO2 nanoparticles(TiO2/AC)were prepared by a properly controlled sol-gel method.The effects of activated carbons(AC)support on inactivated properties of TiO2 nanoparticles were evaluated by photocatalytic inactivation experiments of Escherichia coli.The key factors affecting the inactivation effciency were investigated,including electric power of lamp, temperature,and pH values.The results show that the TiO2/AC composites have high inactivation properties of E.coli in compari...
基金The State Education Ministry "211" Project, the Natural Science Foundation of the Education Commission of Jiangsu Province(2005103TSJB156) and the Funding of the Environment Friendship Laboratory of Nanjing Normal University
文摘TiO2 sol was prepared by sol-gel technique with tetrabutyl titanate as precursor. Supported TiO2 catalysts on activated carbon were prepared by soak and sintering method. The aggregation of nano-TiO2 particles can be effectively suppressed by added polyethylene glycol （PEG） as a surface modifier. The average particle diameter of TiO2, specific surface area and absorbability of catalyst can be modified. Based on characteristics of the TiO2 photocatalyst with XRD, specific surface area, adsorption valves of methylene blue and the amount of TiO2 supported on the activated carbon, the photocatalytic degradation of L-acid was studied. The effect of the factors, such as pH of the solution, the initial concentration of L-acid on the photocatalytic degradation of L-acid, were studied also. It was found that when the pH of the solution is 1.95, the amount of photocatalyst is 0.5 g, the concentration of the L-acid solution is 1.34×10^3 mol/L and the illumination time is 7 h, the photocatalytic degradation efficiency of L-acid can reach 89,88%, The catalyst was reused 6 times and its degradation efficiency hardly changed.
基金Supported by the Science &Technical Ministry of China( No.2 0 0 1BA3 2 2 C) ,the Science &Technical Department ofFujian Province( No.2 0 0 0 F0 0 2 ) and the Science &Technical Development Foundation of Fuzhou U niversity( No.XKJQD-0 10 2 )
文摘Ten kinds of activated carbon from different raw materials were used as supports to prepare ruthenium catalysts. N_2 physisorption and CO chemisorption were carried out to investigate the pore size distribution and the ruthenium dispersion of the catalysts. It was found that the Ru dispersion of the catalyst was closely related to not only the texture of carbon support but also the purity of activated carbon. The activities of a series of the carbon-supported barium-promoted Ru catalysts for ammonia synthesis were measured at 425 ℃, 10 0 MPa and 10 000 h -1. The result shows that the same raw material activated carbon, with a high purity, high surface area, large pore volume and reasonable pore size distribution might disperse ruthenium and promoter sufficiently, which activated carbon as support, could be used to manufacture ruthenium catalyst with a high activity for ammonia synthesis. The different raw material activated carbon as the support would greatly influence the catalytic properties of the ruthenium catalyst for ammonia synthesis. For example, with coconut shell carbon(AC1) as the support, the ammonia concentration in the effluent was 13 17% over 4%Ru-BaO/AC1 catalyst, while with the desulfurized coal carbon(AC10) as the support, that in the effluent was only 1 37% over 4%Ru-BaO/AC10 catalyst.
基金Supported by the National Natural Science Foundation of China (No. 20263003)Natural Science Foundation of Jiangxi province (No. 0250009)
文摘A carbon nanotube-supported NiP amorphous catalyst （NiP/CNT） was prepared by induced reduction. Benzene hydrogenation was used as a probe reaction for the study of catalytic activity. The effects of the support on the activity and thermal stability of the supported catalyst were discussed based on various characterizations, including XRD, TEM, ICP, XPS, H2-TPD, and DTA. In comparison with the NiP amorphous alloy, the benzene conversion on NiP/CNT catalyst was lower, but the specific activity of NiP/CNT was higher, which is attributed to the dispersion produced by the support, an electron-donating effect, and the hydrogen-storage ability of CNT. The NiP/CNT thermal stability was improved because of the dispersion and electronic effects and the good heat-conduction ability of the CNT support.
基金supported by the Natural Science Foundation of China(91645115 and 21473003)High-level talents funding project of Hebei(CL201601,E2016100015)science technology research and development guidance program project of Baoding City(No.16ZF027)
文摘Carbon-supported copper catalyst was prepared for the first time in one-step with copper nitrate and corn stalk through calcination under different temperatures. Uniformly dispersed nanoparticles were obtained and were identified to be Cu（0） and Cu（Ⅰ） in XRD patterns. Excellent catalytic activity and selectivity were achieved in the N-arylation of pyrazole under ligand and protection gas free conditions. About90.4% of product yield was achieved with only 0.5 mol% of copper catalyst（Cu-C-300）, which was considerably more efficient than previous reports. XPS results suggested that the N-arylation of pyrazole activity was closely related to the surface Cu（Ⅰ） species.
