A simple one-pot method was developed to prepare Pt Ni alloy nanoparticles,which can be self-decorated on multiwalled carbon nanotubes in [BMIm][BF4] ionic liquid.The nanohybrids are targeting stable nanocatalysts for...A simple one-pot method was developed to prepare Pt Ni alloy nanoparticles,which can be self-decorated on multiwalled carbon nanotubes in [BMIm][BF4] ionic liquid.The nanohybrids are targeting stable nanocatalysts for fuel cell applications.The sizes of the supported Pt Ni nanoparticles are uniform and as small as 1–2 nm.Pt-to-Ni ratio was controllable by simply selecting a Pt Ni alloy target.The alloy nanoparticles with Pt-to-Ni ratio of 1:1 show high catalytic activity and stability for methanol electro-oxidation.The performance is much higher compared with those of both Pt-only nanoparticles and commercial Pt/C catalyst.The electronic structure characterization on the Pt Ni nanoparticles demonstrates that the electrons are transferred from Ni to Pt,which can suppress the CO poisoning effect.展开更多
Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying de...Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying degree of the object substance, which lead to a great positive impact on its properties. In this work, three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction （XRD） and Transmission electron microscopy （TEM）. The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry （CV） and Chronoamperometry （CA）. Pt-Ru/C catalyst prepared in H2O or binary solvents of H2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems, Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity, lower onset and peak potentials, compared with the above catalysts. Moreover, the catalyst prepared in ternary solvents of isopropanol, water and tetrahydrofuran had the smallest particle size, and the high alloying degree and the dispersion kept unchanged. Therefore, this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.展开更多
Pd@Ru bimetallic nanoparticles deposited on carbon black electro-catalysts have been fabricated by microwave-assisted polyol reduction method and investigated for methanol electro-oxidation （MEO）. The structure and ...Pd@Ru bimetallic nanoparticles deposited on carbon black electro-catalysts have been fabricated by microwave-assisted polyol reduction method and investigated for methanol electro-oxidation （MEO）. The structure and electro-catalytic properties of the as-prepared catalysts were characterized by XRD, SEM, TEM and cyclic voltammetry （CV） techniques. The results showed that the introduction of Ru element （2-10 wt%） into Pd 20 wt%/C （hereafter, denoted as Pd/C） produced a series of core-shell structured binary catalysts. Pd@Ru 5 wt%/C （hereafter, denoted as Pd@Rus/C） catalyst displayed the highest catalytic activity towards MEO. And the mass activity of Pd@Ru5/C electrode catalyst at E = -0.038 V （vs. Hg/HgO） was 1.42 times higher than that of Pd/C electrode catalyst. In addition, the relationship between the catalytic stability for MEO on Pd@Ru/C catalysts and the value of dbp/dfp （the ratio of MEO peak current density in the negative scan and positive scan） were also investigated. The result demonstrated that Pd@Rus/C offering the smallest value of Jbp/Jfp displayed the best stable catalytic performance.展开更多
Carbon nanotubes-Nafion （CNTs-Nation） composites were prepared by impregnated CNTs with Nation in ethanol solution and characterized by FT-IR. Pt-Ru catalysts supported on CNTs-Nafion composites were synthesized by ...Carbon nanotubes-Nafion （CNTs-Nation） composites were prepared by impregnated CNTs with Nation in ethanol solution and characterized by FT-IR. Pt-Ru catalysts supported on CNTs-Nafion composites were synthesized by microwave-assisted polyol process. The physical and electrochemical properties of the catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, CO stripping voltammetry, cyclic voltammetry （CV） and chronoamperometry （CA）. The results showed that the Nation incorporation in CNTs-Nation composites did not significantly alter the oxygen-containing groups on the CNTs surface. The Pt-Ru catalyst supported on CNTs-Nafion composites with 2 wt% Naton showed good dispersion and the best CO oxidation and methanol electro-oxidation activities.展开更多
A novel Pt@ZnO nanorod/carbon fiber （NR/CF） with hierarchical structure was prepared by atomic layer deposition combined with hydrothermal synthesis and magnetron sputtering （MS）. The morphology of Pt changes from...A novel Pt@ZnO nanorod/carbon fiber （NR/CF） with hierarchical structure was prepared by atomic layer deposition combined with hydrothermal synthesis and magnetron sputtering （MS）. The morphology of Pt changes from nanoparticle to nanorod bundle with controlled thickness of Pt between 10 and 50 nm. Significantly, with the increase of voltage from 0 to 0.6 V （vs. standard calomel electrode）, the prompt photocurrent generated on ZnO NR/CF increases from 0235 to 0.725 mA. Besides, the Pt@ZnO NR/CF exhibited higher electrochemical active surface area （ECSA） value, better methanol oxidation ability and CO tolerance than Pt@CF, which demonstrated the importance of the multifunctional ZnO support. As the thickness of Pt increasing from 10 to 50 rim, the ECSA values were improved proportionally, leading to the improvement of methanol oxidation ability. More importantly, UV radiation increased the density of peak current of Pt@ZnO NR/CF towards methanol oxidation by additional 42.4%, which may be due to the synergy catalysis of UV light and electricity.展开更多
The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution （0.1 mol/L）. The catalysts were prepared by cycling the graphite electrode...The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution （0.1 mol/L）. The catalysts were prepared by cycling the graphite electrode in solutions containing Ni, Cu and Co ions at cathodic potentials. The synergistic effects and catalytic activity of the modified electrodes were investigated by cyclic voltammetry （CV）, chronoamperometry CCA） and electrochemical impedance spectroscopy （EIS）. It was found that, in the presence of methanol, the modified Ni-based ternary alloy electrode （G/NiCuCo） exhibited a significantly higher response for methanol oxidation compared to the other samples. The anodic peak currents showed a linear dependency on the square root of the scan rate, which is a characteristic of a diffusion controlled process. During CA studies, the reaction exhibited Cottrellin behavior and the diffusion coefficient of methanol was determined to be 6.25× 10-6 cm2/s and the catalytic rate constant, K, for methanol oxidation was found to be 40×107 cm3/Cmol.s）. EIS was used to investigate the catalytic oxidation of methanol on the surface of the modified electrode.展开更多
PtSn2-SnO2/C nanocatalyst was prepared by co-reduction of Pt and Sn precursor at ca,15℃.The formation of PtSn2-SnO2 nanoparticle was determined by XRD,TEM and XPS characterization.This PtSn2-SnO2/C nanocatalyst exhib...PtSn2-SnO2/C nanocatalyst was prepared by co-reduction of Pt and Sn precursor at ca,15℃.The formation of PtSn2-SnO2 nanoparticle was determined by XRD,TEM and XPS characterization.This PtSn2-SnO2/C nanocatalyst exhibits stronger resistance to CO poisoning and effectively improves methanol electro-catalytic effect,up to 3 times than the commercial Pt/C catalyst.展开更多
Carbon nanotubes （CNTs） supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of ...Carbon nanotubes （CNTs） supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction （XRD） and energy dispersive X-ray （EDX） analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy （EIS）, linear sweep voltammetries （LSV）, and chronoamperometry （CA）. The results show that the catalysts exhibit face-centered cubic （fcc） structure. The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.展开更多
ZnO doped Pt/CeO2 nanocomposites were prepared by electrospinning and reduction impregnation.Xray diffraction（XRD）,transmission electron microscopy（TEM）,energy disperse spectroscopy（EDS） and X-ray photoelectron ...ZnO doped Pt/CeO2 nanocomposites were prepared by electrospinning and reduction impregnation.Xray diffraction（XRD）,transmission electron microscopy（TEM）,energy disperse spectroscopy（EDS） and X-ray photoelectron spectroscopy（XPS） were employed to characterize the nanocomposites.It is observed that ZnO and CeO2 form the hexagonal wurtzite phase and cubic fluorite phase in the nanocomposite,respectively,whilst Pt nanoparticles（NPs） with the number-averaged size of ca.3.1 nm are uniformly distributed on the surface of nanofibers.The mass fraction of Pt NPs in the nanocomposites is about 10 wt%.The doping of ZnO is effective to promote reactive oxygen species,surface reaction sites and the interaction between Pt and oxides.The catalytic performance of nanocomposites was evaluated by the methanol electro-oxidation.indexed with the catalytic activity,stability of catalyst.As a result,it is found that the nanocomposite exhibits much higher activity and stability for methanol oxidation than the undoped Pt/CeO2 catalyst.展开更多
Three-dimensionally（3D） ordered mesoporous carbon sphere arrays（OMCS） are explored to support high loading（60 wt%） Pt nanoparticles as electrocatalysts for the methanol oxidation reaction（MOR）.The OMCS has a u...Three-dimensionally（3D） ordered mesoporous carbon sphere arrays（OMCS） are explored to support high loading（60 wt%） Pt nanoparticles as electrocatalysts for the methanol oxidation reaction（MOR）.The OMCS has a unique hierarchical nanostructure with ordered large mesopores and macropores that can facilitate high dispersion of the Pt nanoparticles and fast mass transport during the reactions. The prepared Pt/OMCS exhibits uniformly dispersed Pt nanoparticles with an average size of- 2.0 nm on the mesoporous walls of the carbon spheres. The Pt/OMCS catalyst shows significantly enhanced specific electrochemically active surface area（ECSA）（73.5 m^2g^-1） and electrocatalytic activity（0.69 mA cm^-2）for the MOR compared with the commercial 60 wt% Pt/C catalyst.展开更多
A λ-MnO2 supported Pt nanocatalyst（5 wt.% Pt/λ-MnO2） was synthesized using a facile approach.X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, scanning electronic microscope（SEM）, transmission e...A λ-MnO2 supported Pt nanocatalyst（5 wt.% Pt/λ-MnO2） was synthesized using a facile approach.X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, scanning electronic microscope（SEM）, transmission electron microscopy（TEM）, and energy disperse spectroscopy（EDS） were used for catalyst structure and morphology characterization, which showed that the metallic Pt particles were attached on a λ-MnO2 surface through the interaction between Pt and λ-MnO2.Cyclic voltammetry（CV） was used to test the catalytic activity of Pt/λ-MnO2 toward methanol oxidation, which showed that Pt/λ-MnO2 catalyst has much higher catalytic activity than baseline Pt/C catalyst.展开更多
Converting methanol to high-value formate through electrochemical methods can significantly reduce the energy consumption associated with conventional production processes.In this study,we directly synthesized iron-do...Converting methanol to high-value formate through electrochemical methods can significantly reduce the energy consumption associated with conventional production processes.In this study,we directly synthesized iron-doped cobalt phosphate(Fe-CoPO)on nickel foam(NF)to achieve excellent activity for the methanol electro-oxidation reaction(MOR).Our results demonstrated that Fe-CoPO produced a current density of 100 mA·cm^(−2)at a significantly low operating potential of 1.436 V(vs.reversible hydrogen electrode(RHE))and operated steadily for 16 h at this current density with a Faradaic efficiency(FE)of 97%.Furthermore,Fe-CoPO maintained a high FE of 100%even at an extremely high current density of 300 mA·cm^(−2)for 8 h.We found that the high MOR activity of Fe-CoPO results from electrochemical reconstruction to generate the Co^(2+/3+)-O bond.The heterogeneous interface between Fe and Co inhibits the formation of Co^(4+),which significantly enhances the MOR activity.Thus,this work not only provides insights into the mechanism of MOR over Co-based catalysts but also offers a novel direction for developing highly active MOR catalysts.展开更多
Pt：Pd：Co ternary alloy nanoparticles were synthesized by sodium borohydride reduction under nitrogen, and were supported on carbon black as catalysts for methanol and formic acid electro-oxidation. Compared with Pt0...Pt：Pd：Co ternary alloy nanoparticles were synthesized by sodium borohydride reduction under nitrogen, and were supported on carbon black as catalysts for methanol and formic acid electro-oxidation. Compared with Pt0.65C00.35/C, Pt/C, Pd0.65C00.35/C, and Pd/C catalyst, Pt0.35Pd0.35Co0.30/C exhibited relatively high durability and strong poisoning resistance, and the Pt-mass activity was 3.6 times higher than that of Pt/C in methanol oxidation reaction. Meanwhile, the Pt0.35Pd0.35Co0.30/C exhibited excellent activity with higher current density and higher CO tolerance than that of Pt0.6sCo0.35/C, Pt/C, Pd0.65C00.35/ C, and Pd/C in formic acid electro-oxidation.展开更多
Heterogeneous nanocomposites comprising chemically distinct constituents are particularly promising in electrocatalysis.We herein report a synthetic strategy that combines the reduction of Pt and Co ionic precursors a...Heterogeneous nanocomposites comprising chemically distinct constituents are particularly promising in electrocatalysis.We herein report a synthetic strategy that combines the reduction of Pt and Co ionic precursors at an appropriate ratio with the subsequent phosphating at an elevated temperature for forming heterogeneous nanocomposites consisting of quasi-spherical Pt_(3)Co alloy domains and rod-like CoP_(2) domains for high-efficiency methanol electrooxidation.The strong electronic coupling between Pt_(3)Co and CoP_(2) domains in the nanocomposites render the electron density around Pt atoms to decrease,which is favorable for reducing the adsorption of poisoning CO-like intermediates on the catalyst surfaces.Accordingly,the as-prepared heterogeneous Pt_(3)Co–CoP_(2) nanocomposites show good performance for methanol electrooxidation both in acidic and alkaline media.In specific,at a Pt loading of only 6.4%on a common carbon substrate,the mass-based activity of Pt_(3)Co–CoP_(2) nanocomposites in an acidic medium is about 2 and 1.5 times as high as that of commercial Pt/C catalyst(20%mass loading)and home-made Pt_(3)Co alloy nanoparticles(8.0%mass loading),while in the alkaline medium,these values are 3 and 2,respectively.展开更多
Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol.Noble metal-based electrocatalysts,which have been extensively studied for the methanol oxidation reaction,can cata...Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol.Noble metal-based electrocatalysts,which have been extensively studied for the methanol oxidation reaction,can catalyze the complete oxidation of methanol to carbon dioxide,but not the mild oxidation to formate.As a result,exploring efficient and earth-abundant electrocatalysts for formate production from methanol is of interest.Herein,we present the electro-oxidation of methanol to formate,catalyzed by iron-substituted lanthanum cobaltite(LaCo_(1-x)Fe_(x)O_(3)).The Fe/Co ratio in the oxides greatly influences the activity and selectivity.This effect is attributed to the higher affinity of Fe and Co to the two reactants:CH3OH and OH,respectively.Because a balance between these affinities is favored,LaCo_(0.5)Fe_(0.5)O_(3) shows the highest formate production rate,at 24.5 mmol h^(-1) g_(oxide)^(-1),and a relatively high Faradaic efficiency of 44.4%in a series of(LaCo_(1-x)Fe_(x)O_(3))samples(x=0.00,0.25,0.50,0.75,1.00)at 1.6 V versus a reversible hydrogen electrode.展开更多
The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation...The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.展开更多
Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active...Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.展开更多
The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,...The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,Pd and Ru) modified Cu/alkalized sepiolite(CuX/SEPA) catalysts were prepared and used for the DOMM in a gas-phase system at low temperatures.The CuRu/SEPA exhibited the highest methanol production of 53 μmol·g^(-1)·h^(-1) and methanol selectivity of 90% under the optimal reaction conditions.Various characterizations demonstrated that the addition of Ru promoted the formation of Cu^(2+)and the contraction of Cu—Si/Al bonds to reduce the distance between framework Al atoms of SEPA to further generate more Al pairs,which facilitated the formation of reactive dicopper species([Cu_(2)O]^(2+)or [Cu_(2)O_(2)]^(2+)).Investigation of the reaction mechanism revealed that [Cu_(2)O]^(2+) or [Cu_(2)O_(2)]^(2+) species could adsorb and activate methane to form CH_(3)O^(*) species and ultimately generated methanol with the assistance of water.展开更多
Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains ...Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains challenging,inhibiting the rational design of excellent FeV-based catalysts.Here,in this work,a series of FeV catalysts with various compositions,including FeVO_(4),isolated VO_(x),low-polymerized V_(n)O_(x),and crystalline V_(2)O_(5) were prepared by controlling the preparation conditions,and were applied to methanol oxidation to formaldehyde reaction.A FeV_(1.1) catalyst,which consisted of FeVO_(4) and low-polymerized V_(n)O_(x) species showed an excellent catalytic performance with a methanol conversion of 92.3%and a formaldehyde selectivity of 90.6%,which was comparable to that of conventional iron-molybdate catalyst.The results of CH_(3)OH-IR,O_(2) pulse and control experiments revealed a crucial synergistic effect between FeVO_(4) and low-polymerized V_(n)O_(x).It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates,contributing to the high catalytic activity and formaldehyde selectivity.This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.展开更多
This work investigates the potential of low-pressure,medium-speed dual-fuel engines for cleaner maritime transportation.The thermodynamic performance of these engines is explored using three alternative fuels:liquefie...This work investigates the potential of low-pressure,medium-speed dual-fuel engines for cleaner maritime transportation.The thermodynamic performance of these engines is explored using three alternative fuels:liquefied natural gas(LNG),methanol,and ammonia.A parametric analysis examines the effect of adjustments to key engine parameters(compression ratio,boost pressure,and air-fuel ratio)on performance.Results show an initial improvement in performance with an increase in compression ratio,which reaches a peak and then declines.Similarly,increases in boost pressure and air-fuel ratio lead to linear performance gains.However,insufficient cooling reduces the amount of fuel burned,which hinders performance.Exergy analysis reveals significant exergy destruction within the engine,which ranges from 69.96%(methanol)to 78.48%(LNG).Notably,the combustion process is the leading cause of exergy loss.Among the fuels tested,methanol exhibits the lowest combustion-related exergy destruction(56.41%),followed by ammonia(62.12%)and LNG(73.77%).These findings suggest that methanol is a promising near-term alternative to LNG for marine fuel applications.展开更多
基金supported by the National Natural Science Foundation of China(No.61274019)the Soochow University-Western University Joint Centre for Synchrotron Radiation Research+1 种基金the Collaborative Innovation Center of Suzhou Nano Science & Technologythe Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)
文摘A simple one-pot method was developed to prepare Pt Ni alloy nanoparticles,which can be self-decorated on multiwalled carbon nanotubes in [BMIm][BF4] ionic liquid.The nanohybrids are targeting stable nanocatalysts for fuel cell applications.The sizes of the supported Pt Ni nanoparticles are uniform and as small as 1–2 nm.Pt-to-Ni ratio was controllable by simply selecting a Pt Ni alloy target.The alloy nanoparticles with Pt-to-Ni ratio of 1:1 show high catalytic activity and stability for methanol electro-oxidation.The performance is much higher compared with those of both Pt-only nanoparticles and commercial Pt/C catalyst.The electronic structure characterization on the Pt Ni nanoparticles demonstrates that the electrons are transferred from Ni to Pt,which can suppress the CO poisoning effect.
基金supported by 863 Project(No.2006AA05Z102)the Cultivation Fund of the Key Scientific and Technical Innovation Project,Ministry of Education of China (No.707050)+1 种基金Specialized Research Fund for the Doctoral Program of Higher Education (No.20060610023)Chengdu Natural Science Foundation (Nos.06GGYB449GX-030,and 07GGZD139GX)
文摘Alloying degree, particle size and the level of dispersion are the key structural parameters of Pt-Ru/C catalyst in fuel cells. Solvent（s） used in the preparation process can affect the particle size and alloying degree of the object substance, which lead to a great positive impact on its properties. In this work, three types of solvents and their mixtures were used in preparation of the Pt-Ru/C catalysts by chemical reduction of metal precursors with sodium borohydride at room temperature. The structure of the catalysts was characterized by X-ray diffraction （XRD） and Transmission electron microscopy （TEM）. The catalytic activity and stability for methanol electro-oxidation were studied by Cyclic Voltammetry （CV） and Chronoamperometry （CA）. Pt-Ru/C catalyst prepared in H2O or binary solvents of H2O and isopropanol had large particle size and low alloying degree leading to low catalytic activity and less stability in methanol electro-oxidation. When tetrahydrofuran was added to the above solvent systems, Pt-Ru/C catalyst prepared had smaller particle size and higher alloying degree which resulted in better catalytic activity, lower onset and peak potentials, compared with the above catalysts. Moreover, the catalyst prepared in ternary solvents of isopropanol, water and tetrahydrofuran had the smallest particle size, and the high alloying degree and the dispersion kept unchanged. Therefore, this kind of catalyst showed the highest catalytic activity and good stability for methanol electro-oxidation.
基金supported by the National Basic Research Program of China(2013CB934001)the Natural Science Foundation of Beijing(2051001)the Natural Science Foundation of China(51074011)
文摘Pd@Ru bimetallic nanoparticles deposited on carbon black electro-catalysts have been fabricated by microwave-assisted polyol reduction method and investigated for methanol electro-oxidation （MEO）. The structure and electro-catalytic properties of the as-prepared catalysts were characterized by XRD, SEM, TEM and cyclic voltammetry （CV） techniques. The results showed that the introduction of Ru element （2-10 wt%） into Pd 20 wt%/C （hereafter, denoted as Pd/C） produced a series of core-shell structured binary catalysts. Pd@Ru 5 wt%/C （hereafter, denoted as Pd@Rus/C） catalyst displayed the highest catalytic activity towards MEO. And the mass activity of Pd@Ru5/C electrode catalyst at E = -0.038 V （vs. Hg/HgO） was 1.42 times higher than that of Pd/C electrode catalyst. In addition, the relationship between the catalytic stability for MEO on Pd@Ru/C catalysts and the value of dbp/dfp （the ratio of MEO peak current density in the negative scan and positive scan） were also investigated. The result demonstrated that Pd@Rus/C offering the smallest value of Jbp/Jfp displayed the best stable catalytic performance.
基金supported by National Natural Science Foundation of China (NO.0576023)Key Project of Science and Technology Department of Guangdong Province (NO.2008B010800036 NO.2008B010800037)
文摘Carbon nanotubes-Nafion （CNTs-Nation） composites were prepared by impregnated CNTs with Nation in ethanol solution and characterized by FT-IR. Pt-Ru catalysts supported on CNTs-Nafion composites were synthesized by microwave-assisted polyol process. The physical and electrochemical properties of the catalysts were characterized by X-ray diffraction （XRD）, transmission electron microscope （TEM）, CO stripping voltammetry, cyclic voltammetry （CV） and chronoamperometry （CA）. The results showed that the Nation incorporation in CNTs-Nation composites did not significantly alter the oxygen-containing groups on the CNTs surface. The Pt-Ru catalyst supported on CNTs-Nafion composites with 2 wt% Naton showed good dispersion and the best CO oxidation and methanol electro-oxidation activities.
基金Supported by the National Key R&D Program(2016YFC0204000)the National Natural Science Foundation of China(U1510202)+1 种基金the Jiangsu Province Scientific Supporting Project(BK20170046and BE2015023)
文摘A novel Pt@ZnO nanorod/carbon fiber （NR/CF） with hierarchical structure was prepared by atomic layer deposition combined with hydrothermal synthesis and magnetron sputtering （MS）. The morphology of Pt changes from nanoparticle to nanorod bundle with controlled thickness of Pt between 10 and 50 nm. Significantly, with the increase of voltage from 0 to 0.6 V （vs. standard calomel electrode）, the prompt photocurrent generated on ZnO NR/CF increases from 0235 to 0.725 mA. Besides, the Pt@ZnO NR/CF exhibited higher electrochemical active surface area （ECSA） value, better methanol oxidation ability and CO tolerance than Pt@CF, which demonstrated the importance of the multifunctional ZnO support. As the thickness of Pt increasing from 10 to 50 rim, the ECSA values were improved proportionally, leading to the improvement of methanol oxidation ability. More importantly, UV radiation increased the density of peak current of Pt@ZnO NR/CF towards methanol oxidation by additional 42.4%, which may be due to the synergy catalysis of UV light and electricity.
基金provided by K.N.Toosi University of Technology Research Council to conduct this research
文摘The electrocatalytic oxidation of methanol was studied over Ni, Co and Cu binary or ternary alloys on graphite electrodes in a NaOH solution （0.1 mol/L）. The catalysts were prepared by cycling the graphite electrode in solutions containing Ni, Cu and Co ions at cathodic potentials. The synergistic effects and catalytic activity of the modified electrodes were investigated by cyclic voltammetry （CV）, chronoamperometry CCA） and electrochemical impedance spectroscopy （EIS）. It was found that, in the presence of methanol, the modified Ni-based ternary alloy electrode （G/NiCuCo） exhibited a significantly higher response for methanol oxidation compared to the other samples. The anodic peak currents showed a linear dependency on the square root of the scan rate, which is a characteristic of a diffusion controlled process. During CA studies, the reaction exhibited Cottrellin behavior and the diffusion coefficient of methanol was determined to be 6.25× 10-6 cm2/s and the catalytic rate constant, K, for methanol oxidation was found to be 40×107 cm3/Cmol.s）. EIS was used to investigate the catalytic oxidation of methanol on the surface of the modified electrode.
基金supported by NSFC (Nos. 21373116 and 21421001)the Tianjin Natural Science Research Fund (No. 13JCYBJC18300)+1 种基金RFDP (No. 20120031110005)the MOE Innovation Team (No. IRT13022) of China
文摘PtSn2-SnO2/C nanocatalyst was prepared by co-reduction of Pt and Sn precursor at ca,15℃.The formation of PtSn2-SnO2 nanoparticle was determined by XRD,TEM and XPS characterization.This PtSn2-SnO2/C nanocatalyst exhibits stronger resistance to CO poisoning and effectively improves methanol electro-catalytic effect,up to 3 times than the commercial Pt/C catalyst.
基金The project is supported by the National Natural Science Foundation of China (20576023)the Science and Technology Project of Guangzhou City (2005 J1-C0361)the Key Project of Education Bureau of Guangzhou City (2052).
文摘Carbon nanotubes （CNTs） supported Pt-Ru and Pt-Ru-Ni catalysts were prepared by chemical reduction of metal precursors with sodium borohydride at room temperature. The crystallographic properties and composition of the catalysts were characterized by X-ray diffraction （XRD） and energy dispersive X-ray （EDX） analysis, and the catalytic activity and stability for methanol electro-oxidation were measured by electrochemical impedance spectroscopy （EIS）, linear sweep voltammetries （LSV）, and chronoamperometry （CA）. The results show that the catalysts exhibit face-centered cubic （fcc） structure. The particle size of Pt-Ru-Ni/CNTs catalyst is about 4.8 nm. The catalytic activity and stability of the Pt-Ru-Ni/CNTs catalyst are higher than those of Pt-Ru/CNTs catalyst.
基金Project supported by the National Natural Science Foundation of China(21475021,21427807)the Natural Science Foundation of Jiangsu Province(BK20141331)the Priority Academic Program Development of Jiangsu Higher Education Institutions
文摘ZnO doped Pt/CeO2 nanocomposites were prepared by electrospinning and reduction impregnation.Xray diffraction（XRD）,transmission electron microscopy（TEM）,energy disperse spectroscopy（EDS） and X-ray photoelectron spectroscopy（XPS） were employed to characterize the nanocomposites.It is observed that ZnO and CeO2 form the hexagonal wurtzite phase and cubic fluorite phase in the nanocomposite,respectively,whilst Pt nanoparticles（NPs） with the number-averaged size of ca.3.1 nm are uniformly distributed on the surface of nanofibers.The mass fraction of Pt NPs in the nanocomposites is about 10 wt%.The doping of ZnO is effective to promote reactive oxygen species,surface reaction sites and the interaction between Pt and oxides.The catalytic performance of nanocomposites was evaluated by the methanol electro-oxidation.indexed with the catalytic activity,stability of catalyst.As a result,it is found that the nanocomposite exhibits much higher activity and stability for methanol oxidation than the undoped Pt/CeO2 catalyst.
基金financial support from the National Natural Science Foundation of China (No. 51172014)the National 973 Program of China (No. 2009CB219903)the Scientific Innovation Grant for Excellent Young Scientists of Hebei University of Technology (No. 2015001)
文摘Three-dimensionally（3D） ordered mesoporous carbon sphere arrays（OMCS） are explored to support high loading（60 wt%） Pt nanoparticles as electrocatalysts for the methanol oxidation reaction（MOR）.The OMCS has a unique hierarchical nanostructure with ordered large mesopores and macropores that can facilitate high dispersion of the Pt nanoparticles and fast mass transport during the reactions. The prepared Pt/OMCS exhibits uniformly dispersed Pt nanoparticles with an average size of- 2.0 nm on the mesoporous walls of the carbon spheres. The Pt/OMCS catalyst shows significantly enhanced specific electrochemically active surface area（ECSA）（73.5 m^2g^-1） and electrocatalytic activity（0.69 mA cm^-2）for the MOR compared with the commercial 60 wt% Pt/C catalyst.
基金supported by the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality, Beijing Natural Science Foundation (No. 207001)the Major State Basic Research and Development Program of China (No. 2002CB211807)
文摘A λ-MnO2 supported Pt nanocatalyst（5 wt.% Pt/λ-MnO2） was synthesized using a facile approach.X-ray diffraction（XRD）, X-ray photoelectron spectroscopy（XPS）, scanning electronic microscope（SEM）, transmission electron microscopy（TEM）, and energy disperse spectroscopy（EDS） were used for catalyst structure and morphology characterization, which showed that the metallic Pt particles were attached on a λ-MnO2 surface through the interaction between Pt and λ-MnO2.Cyclic voltammetry（CV） was used to test the catalytic activity of Pt/λ-MnO2 toward methanol oxidation, which showed that Pt/λ-MnO2 catalyst has much higher catalytic activity than baseline Pt/C catalyst.
基金support from the National Key Research and Development Program of China(No.2022YFC3703503)the Science and Technology Commission of Shanghai Municipality(No.24ZR1416000)the Japan Society for the Promotion of Science(JSPS)through Grant-in-Aid for Scientific Research(Nos.22H00282 and 23K26456).
文摘Converting methanol to high-value formate through electrochemical methods can significantly reduce the energy consumption associated with conventional production processes.In this study,we directly synthesized iron-doped cobalt phosphate(Fe-CoPO)on nickel foam(NF)to achieve excellent activity for the methanol electro-oxidation reaction(MOR).Our results demonstrated that Fe-CoPO produced a current density of 100 mA·cm^(−2)at a significantly low operating potential of 1.436 V(vs.reversible hydrogen electrode(RHE))and operated steadily for 16 h at this current density with a Faradaic efficiency(FE)of 97%.Furthermore,Fe-CoPO maintained a high FE of 100%even at an extremely high current density of 300 mA·cm^(−2)for 8 h.We found that the high MOR activity of Fe-CoPO results from electrochemical reconstruction to generate the Co^(2+/3+)-O bond.The heterogeneous interface between Fe and Co inhibits the formation of Co^(4+),which significantly enhances the MOR activity.Thus,this work not only provides insights into the mechanism of MOR over Co-based catalysts but also offers a novel direction for developing highly active MOR catalysts.
基金supported by NSFC(No.21373116)Tianjin Natural Science Research Fund(No.13JCYBJC18300)+1 种基金RFDP(No. 20120031110005)MOE Innovation Team of China(No. IRT13022)
文摘Pt：Pd：Co ternary alloy nanoparticles were synthesized by sodium borohydride reduction under nitrogen, and were supported on carbon black as catalysts for methanol and formic acid electro-oxidation. Compared with Pt0.65C00.35/C, Pt/C, Pd0.65C00.35/C, and Pd/C catalyst, Pt0.35Pd0.35Co0.30/C exhibited relatively high durability and strong poisoning resistance, and the Pt-mass activity was 3.6 times higher than that of Pt/C in methanol oxidation reaction. Meanwhile, the Pt0.35Pd0.35Co0.30/C exhibited excellent activity with higher current density and higher CO tolerance than that of Pt0.6sCo0.35/C, Pt/C, Pd0.65C00.35/ C, and Pd/C in formic acid electro-oxidation.
基金supported by the Beijing Natural Science Foundation(Grant No.Z200012)National Natural Science Foundation of China(Grant Nos.22075290,21972068,21776292,21706265)+1 种基金State Key Laboratory of Multiphase Complex Systems,Institute of Process Engineering,Chinese Academy of Sciences(MPCS-2019-A-09)Nanjing IPE Institute of Green Manufacturing Industry are gratefully acknowledged.
文摘Heterogeneous nanocomposites comprising chemically distinct constituents are particularly promising in electrocatalysis.We herein report a synthetic strategy that combines the reduction of Pt and Co ionic precursors at an appropriate ratio with the subsequent phosphating at an elevated temperature for forming heterogeneous nanocomposites consisting of quasi-spherical Pt_(3)Co alloy domains and rod-like CoP_(2) domains for high-efficiency methanol electrooxidation.The strong electronic coupling between Pt_(3)Co and CoP_(2) domains in the nanocomposites render the electron density around Pt atoms to decrease,which is favorable for reducing the adsorption of poisoning CO-like intermediates on the catalyst surfaces.Accordingly,the as-prepared heterogeneous Pt_(3)Co–CoP_(2) nanocomposites show good performance for methanol electrooxidation both in acidic and alkaline media.In specific,at a Pt loading of only 6.4%on a common carbon substrate,the mass-based activity of Pt_(3)Co–CoP_(2) nanocomposites in an acidic medium is about 2 and 1.5 times as high as that of commercial Pt/C catalyst(20%mass loading)and home-made Pt_(3)Co alloy nanoparticles(8.0%mass loading),while in the alkaline medium,these values are 3 and 2,respectively.
基金This research was supported by the National Research Foundation,Prime Minister's Office,Singapore,under its Campus for Research Excellence and Technological Enterprise(CREATE)programThe work was partially supported by a Singapore Ministry of Education Tier 1 grant(2019-T1-002-125)and Tier 2 grant(MOE-T2EP10220-0001).
文摘Electrochemically producing formate by oxidizing methanol is a promising way to add value to methanol.Noble metal-based electrocatalysts,which have been extensively studied for the methanol oxidation reaction,can catalyze the complete oxidation of methanol to carbon dioxide,but not the mild oxidation to formate.As a result,exploring efficient and earth-abundant electrocatalysts for formate production from methanol is of interest.Herein,we present the electro-oxidation of methanol to formate,catalyzed by iron-substituted lanthanum cobaltite(LaCo_(1-x)Fe_(x)O_(3)).The Fe/Co ratio in the oxides greatly influences the activity and selectivity.This effect is attributed to the higher affinity of Fe and Co to the two reactants:CH3OH and OH,respectively.Because a balance between these affinities is favored,LaCo_(0.5)Fe_(0.5)O_(3) shows the highest formate production rate,at 24.5 mmol h^(-1) g_(oxide)^(-1),and a relatively high Faradaic efficiency of 44.4%in a series of(LaCo_(1-x)Fe_(x)O_(3))samples(x=0.00,0.25,0.50,0.75,1.00)at 1.6 V versus a reversible hydrogen electrode.
基金the Canadian NRCan OERD Energy Innovation Programthe Natural Sciences and Engineering Research Council of Canada,and the Carbon Solution Program for their financial support.
文摘The pursuit of alternative fuel generation technologies has gained momentum due to the diminishing reserves of fossil fuels and global warming from increased CO_(2)emission.Among the proposed methods,the hydrogenation of CO_(2)to produce marketable carbon-based products like methanol and ethanol is a practical approach that offers great potential to reduce CO_(2)emissions.Although significant volumes of methanol are currently produced from CO_(2),developing highly efficient and stable catalysts is crucial for further enhancing conversion and selectivity,thereby reducing process costs.An in-depth examination of the differences and similarities in the reaction pathways for methanol and ethanol production highlights the key factors that drive C-C coupling.Identifying these factors guides us toward developing more effective catalysts for ethanol synthesis.In this paper,we explore how different catalysts,through the production of various intermediates,can initiate the synthesis of methanol or ethanol.The catalytic mechanisms proposed by spectroscopic techniques and theoretical calculations,including operando X-ray methods,FTIR analysis,and DFT calculations,are summarized and presented.The following discussion explores the structural properties and composition of catalysts that influence C-C coupling and optimize the conversion rate of CO_(2)into ethanol.Lastly,the review examines recent catalysts employed for selective methanol and ethanol production,focusing on single-atom catalysts.
基金supported by Research Grant from China Petroleum and Chemical Corp。
文摘Cu/ZnO-based catalysts are widely employed for methanol synthesis via CO_(2) hydrogenation.The preparation procedure is sensitive to the particle size and interfacial structure,which are considered as potential active centers influencing the rate of both methanol and CO formation.The particle size and the interaction between Cu and the support materials are influenced by the coprecipitation conditions,let alone that the mechanistic divergence remains unclear.In this work,a series of Cu/ZnO/ZrO_(2) catalysts were prepared via co-precipitation at different pH value and systematically characterized.The structure has been correlated with kinetic results to establish the structure-performance relationship.Kinetic analysis demonstrates that methanol synthesis follows a single-site Langmuir-Hinshelwood(L-H)mechanism,i.e.,Cu serves as the active site where CO_(2) and H_(2) competitively adsorb and react to form methanol.In contrast,CO formation proceeds via a dual-site L-H mechanism,where CO_(2) adsorbs onto ZnO and H_(2) onto Cu,with the reaction occurring at the Cu/ZnO interface.Therefore,for the direct formation of methanol,solely reducing the particle size of Cu would not be beneficial.
基金financial assistance from the Anhui Provincial Major Science and Technology Project(202003a05020022)the Institute of Energy,Hefei Comprehensive National Science Center(21KZS219)。
文摘The direct oxidation of methane to methanol(DOMM) has been recognized as a significant technology for efficiently utilizing low-concentration coalbed methane(LCMM) and supplying liquid fuel.Herein,the noble metals(Pt,Pd and Ru) modified Cu/alkalized sepiolite(CuX/SEPA) catalysts were prepared and used for the DOMM in a gas-phase system at low temperatures.The CuRu/SEPA exhibited the highest methanol production of 53 μmol·g^(-1)·h^(-1) and methanol selectivity of 90% under the optimal reaction conditions.Various characterizations demonstrated that the addition of Ru promoted the formation of Cu^(2+)and the contraction of Cu—Si/Al bonds to reduce the distance between framework Al atoms of SEPA to further generate more Al pairs,which facilitated the formation of reactive dicopper species([Cu_(2)O]^(2+)or [Cu_(2)O_(2)]^(2+)).Investigation of the reaction mechanism revealed that [Cu_(2)O]^(2+) or [Cu_(2)O_(2)]^(2+) species could adsorb and activate methane to form CH_(3)O^(*) species and ultimately generated methanol with the assistance of water.
文摘Iron-Vanadium(FeV)catalyst showed a unique catalytic activity for the selective oxidation of methanol to formaldehyde;however,due to its complex compositions,the identification of catalytic active sites still remains challenging,inhibiting the rational design of excellent FeV-based catalysts.Here,in this work,a series of FeV catalysts with various compositions,including FeVO_(4),isolated VO_(x),low-polymerized V_(n)O_(x),and crystalline V_(2)O_(5) were prepared by controlling the preparation conditions,and were applied to methanol oxidation to formaldehyde reaction.A FeV_(1.1) catalyst,which consisted of FeVO_(4) and low-polymerized V_(n)O_(x) species showed an excellent catalytic performance with a methanol conversion of 92.3%and a formaldehyde selectivity of 90.6%,which was comparable to that of conventional iron-molybdate catalyst.The results of CH_(3)OH-IR,O_(2) pulse and control experiments revealed a crucial synergistic effect between FeVO_(4) and low-polymerized V_(n)O_(x).It enhanced the oxygen supply capacity and suitable binding and adsorption strengths for formaldehyde intermediates,contributing to the high catalytic activity and formaldehyde selectivity.This study not only advances the understanding of FeV structure but also offers valuable guidelines for selective methanol oxidation to formaldehyde.
文摘This work investigates the potential of low-pressure,medium-speed dual-fuel engines for cleaner maritime transportation.The thermodynamic performance of these engines is explored using three alternative fuels:liquefied natural gas(LNG),methanol,and ammonia.A parametric analysis examines the effect of adjustments to key engine parameters(compression ratio,boost pressure,and air-fuel ratio)on performance.Results show an initial improvement in performance with an increase in compression ratio,which reaches a peak and then declines.Similarly,increases in boost pressure and air-fuel ratio lead to linear performance gains.However,insufficient cooling reduces the amount of fuel burned,which hinders performance.Exergy analysis reveals significant exergy destruction within the engine,which ranges from 69.96%(methanol)to 78.48%(LNG).Notably,the combustion process is the leading cause of exergy loss.Among the fuels tested,methanol exhibits the lowest combustion-related exergy destruction(56.41%),followed by ammonia(62.12%)and LNG(73.77%).These findings suggest that methanol is a promising near-term alternative to LNG for marine fuel applications.
