High-loading Pt/C catalysts play an important role in the fabrication of membrane electrode assemblies with thin catalytic layer,which enhance mass transport and maintain the balance of water and heat.Unfortunately,as...High-loading Pt/C catalysts play an important role in the fabrication of membrane electrode assemblies with thin catalytic layer,which enhance mass transport and maintain the balance of water and heat.Unfortunately,as the loading increases,the agglomeration and growth of Pt nanoparticles(NPs)occur,causing unsatisfactory performance.Here,we present an efficient method for preparing of highly dispersed and small-sized Pt/C catalysts with Pt loadings varying from 39.01 wt%to 66.48 wt%through the high-temperature shock technique.The high density and ultrafine(~2.5 nm)Pt NPs are successfully anchored onto Vulcan XC-72R carbon black without the use of additional capping agents or surfactants.The modified carbon supports enhance the affinity for Pt precursors,contributing to loading efficiencies of 95%or more,while also providing abundant sites for the nucleation and fixation of Pt NPs,thus preventing agglomeration.In the context of the hydrogen evolution reaction in acidic media,the as-synthesized high-loading Pt/C catalysts show remarkable activity and stability,outperforming the state-of-the-art commercial Pt/C.This is mainly because the combined effects of ultrasmall and uniform Pt NPs,optimized electronic structure of Pt site,superhydrophilicity and effective anchoring of Pt NPs.The polymer electrolyte membrane electrolyzer integrated with Pt60/OX72R and commercial IrO2 reaches 1 A cm^(-2)at 1.77 V and operates stably for 120 hours with a negligible voltage decay.This new strategy is fast,scalable and cost-effective for large-scale production of metal-supported catalysts,especially for the high-loading ones.展开更多
It is reported for the first time that the Pt/C catalyst can be prepared with a new and simple organic sol method using SnCl2 as the reductant. It was found that the average size of the Pt particles in the Pt/C cataly...It is reported for the first time that the Pt/C catalyst can be prepared with a new and simple organic sol method using SnCl2 as the reductant. It was found that the average size of the Pt particles in the Pt/C catalysts could be controlled with controlling the preparation conditions. The effect of the average sizes of the Pt particles in the Pt/C catalysts obtained with this method on the electrocatalytical activity of the oxidation of methanol was investigated.展开更多
A series of Pt/C catalysts for proton exchange membrane fuel cells(PEMFCs) with various metal loadings is synthesized by a microwave-assisted polyol process via mixing an extremely stable platinum colloid(> 3 month...A series of Pt/C catalysts for proton exchange membrane fuel cells(PEMFCs) with various metal loadings is synthesized by a microwave-assisted polyol process via mixing an extremely stable platinum colloid(> 3 months’ shelf life) from single batch preparation with activated carbon ethylene glycol suspension.21 wt%, 42 wt% and 61 wt% Pt loadings are employed to showcase the advantages of the improved polyol process. The ultraviolet(UV)–visible spectra and ζ-potential measurements are conducted to monitor the wet chemistry process during catalyst preparation. The powder X-ray diffraction(XRD), transmission electron microscopy(TEM) and thermogravimetric analysis(TGA) characterizations are carried out on catalysts. The catalyst activities are investigated using electrochemical and single cell tests. The stability of Pt nanoparticle colloid is explored by ORR, cyclic voltammetry(CV) and ζ-potential measurements. The TEM results show the Pt particle sizes of the colloid, and the sizes of the 21 wt%, 42 wt% and 61 wt%Pt/C samples are 2.1–3.9 nm. Because of the high Pt dispersion, the Pt/C catalysts exhibit superior electroactivity toward ORR. In addition, four 61 wt% Pt/C catalysts made from the Pt colloid with 0–3 months’ shelf life show almost the same performance, which exhibits superior stability of the Pt colloid system without surfactant protection.展开更多
Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties.Herein,we demonstrate a precise engineering strategy for the carbon s...Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties.Herein,we demonstrate a precise engineering strategy for the carbon surface chemistry of Pt/C catalysts—that is,for the electron-withdrawing/donating oxygencontaining groups on the carbon surface—to fine-tune the electrons of the supported metal nanoparticles.Taking the ammonia borane hydrolysis as an example,a combination of density functional theory(DFT)calculations,advanced characterizations,and kinetics and isotopic analyses reveals quantifiable relationships among the carbon surface chemistry,Pt charge state and binding energy,activation entropy/enthalpy,and resultant catalytic activity.After decoupling the influences of other factors,the Pt charge is unprecedentedly identified as an experimentally measurable descriptor of the Pt active site,contributing to a 15-fold increment in the hydrogen generation rate.Further incorporating the Pt charge with the number of Pt active sites,a mesokinetics model is proposed for the first time that can individually quantify the contributions of the electronic and geometric properties to precisely predict the catalytic performance.Our results demonstrate a potentially groundbreaking methodology to design and manipulate metal–carbon catalysts with desirable properties.展开更多
Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance...Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance of supported metal catalysts.This is particularly true for single-atom catalysts(SACs)and pseudo-single-atom catalysts(pseudo-SACs),where all metal atoms are dispersed on,and interact directly with the support.Consequently,the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts.In this work,we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation.We fabricated CoFe_(2)O_(4) supported Pt pseudo-SACs and nanoparticle catalysts,followed by a straightforward water treatment process.It was found that the covalent strong metal-support interaction(CMSI)in pseudo-SACs can be weakened,leading to a significant activity improvement in methane combustion reaction.This finding aligns with our recent observation of CoFe_(2)O_(4) supported Pt SACs.By contrast,the MSI in Pt nanoparticle catalyst was barely affected by the water treatment,giving rise to almost unchanged catalytic performance.This work highlights the critical role of metal size in determining the MSI modulation,offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.展开更多
The efficient conversion of lignin into mono-cycloalkanes via both C–O and C–C bonds cleavage are attractive,but challenging due to the high C–C bond dissociation energy.Previous studies have demonstrated that NbO_...The efficient conversion of lignin into mono-cycloalkanes via both C–O and C–C bonds cleavage are attractive,but challenging due to the high C–C bond dissociation energy.Previous studies have demonstrated that NbO_(x)-based catalysts exhibited exceptional capabilities for C_(Ar)–C bond cleavage and broken the limitation of lignin monomers.In this work,we presented an economical multifunctional Pt-Nb/MOR catalyst that achieved an impressive monomer yield of 147%during the depolymerization and hydrodeoxygenation of lignin into mono-cycloalkanes.Reaction pathway studies showed that unlike traditional NbO_(x)-based catalytic system,bicyclohexane was an important intermediate in this system and followed the C_(sp3)–C_(sp3)cleavage pathway after complete cyclic-hydrogenation.Deep investigations demonstrated that the doping of Nb in Pt/MOR not only enhanced the activation of hydrogen by Pt,but also increased the acidity of MOR,both of these are favor for the hydrogenolytic cleavage of C_(sp3)–C_(sp3)bonds.This work provides a low-cost catalyst to obtain high-yield monomers from lignin under relatively mild conditions and would help to design catalysts with higher activity for the valorization of lignin.展开更多
Platinum nanoparticles supported on carbons（Pt/C,60%,mass fraction） electrocatalysts for direct methanol fuel cell（DMFC） were prepared by citrate-stabilized method with different reductants and carbon supports.The...Platinum nanoparticles supported on carbons（Pt/C,60%,mass fraction） electrocatalysts for direct methanol fuel cell（DMFC） were prepared by citrate-stabilized method with different reductants and carbon supports.The catalysts were characterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM） and cyclic voltammetry（CV）.It is found that the size of Pt nanoparticles on carbon is controllable by citrate addition and reductant optimization,and the form of carbon support has a great influence on electrocatalytic activity of catalysts.The citrate-stabilized Pt nanoparticles supported on BP2000 carbon,which was reduced by formaldehyde,exhibit the best performance with about 2 nm in diameter and 66.46 m2/g（Pt） in electrocatalytic active surface（EAS） area.Test on single DMFC with 60%（mass fraction） Pt/BP2000 as cathode electrocatalyst showed maximum power density at 78.8 mW/cm2.展开更多
The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO tech...The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO techniques combined with propane dehydrogenation tests.It has been shown that SUZ-4-supported PtSnNa（PtSnNa/SUZ-4） was determined to be a better catalyst for propane dehydrogenation than conventional catalysts supported on ZSM-5,owing to its higher catalytic activity and stability.Dibenzothiophene poisoning experiments were performed to investigate the detailed structures of the two supported catalysts.The characterization of the two catalysts indicates that the distribution of Pt on the porous support affects the activity.In contrast to ZSM-5-supported catalysts,Pt particles on the PtSnNa/SUZ-4 are primarily dispersed over the external surface and are not as readily deactivated by carbon deposition.This is because that the strong acid sites of the SUZ-4 zeolite evidently prevented the impregnation of the Pt precursor H_2PtCl_6 into the zeolite.In contrast,the weak acid sites of the ZSM-5 zeolite led to more of the precursor entering the zeolite tunnels,followed by transformation to highly dispersed Pt clusters during calcination.In the case of the PtSnNa/ZSM-5,the interactions between Sn oxides and the support were lessened,owing to the weaker acidity of the ZSM-5 zeolite.The dispersed Sn oxides were therefore easier to reduce to the metallic state,thus decreasing the catalytic activity for hydrocarbon dehydrogenation.展开更多
Platinum/cerium-zirconium-sulfate（Pt/Ce-Zr-SO_4^（2-）） catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate（SO_4^（2-））addition improv...Platinum/cerium-zirconium-sulfate（Pt/Ce-Zr-SO_4^（2-）） catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate（SO_4^（2-））addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^（2-） with 10 wt%SO_4^（2-）,the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^（2-） support,and the increased number of Pt particles built up more Pt^（-）-（SO_4^（2-））^（-） couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^（2-） with good sulfur resistance.展开更多
A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potenti...A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.展开更多
In this paper, MPt/C (M= La, Nd) catalysts of PEMFC were synthesized by microwave radiation process. The crystallinity and structure of catalysts were respectively analyzed by XRD and nitrogen adsorption tests. The ac...In this paper, MPt/C (M= La, Nd) catalysts of PEMFC were synthesized by microwave radiation process. The crystallinity and structure of catalysts were respectively analyzed by XRD and nitrogen adsorption tests. The activity of catalysts was investigated by electrochemistry experiment. The results showed that: 1) compared with Pt/C catalyst prepared by typical impregnation-reduction process, the size of MPt/C catalyst particle decreased and the available crystal for O2 reduction increased; 2) the MPt/C catalysts had relatively high BET surface areas; and 3)these crystal transformations of the MPt/C catalyst brought high the electrocatalytic activity, and as a result, improved the power of PEMFC.展开更多
A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-co...A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.展开更多
The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the...The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the deep oxidation of VOCs. In comparison with the Pt/CeY, CuMnCe, and CeY monolithic catalysts, the Pt/CuMnCe monolithic catalyst shows an excellent performance for toluene,ethyl acetate,and n-hexane oxidation and the Tis low to 216, 200 and 260 ℃,respectively. The active components Pt/PtO and CuMnCe result in a better synergetic interaction, which promote the catalyst reducibility, increase the oxygen mobility, and enhance the adsorption and activation of organic molecules.展开更多
Reverse water gas shift (RWGS) reaction can serve as a pivotal stage in the CO2 conversion processes, which is vital for the utilization of CO2. In this study, RWGS reaction was performed over Pt/CeO2 catalysts at the...Reverse water gas shift (RWGS) reaction can serve as a pivotal stage in the CO2 conversion processes, which is vital for the utilization of CO2. In this study, RWGS reaction was performed over Pt/CeO2 catalysts at the temperature range of 200-500 degrees C under ambient pressure. Compared with pure CeO2, Pt/CeO2 catalysts exhibited superior RWGS activity at lower reaction temperature. Meanwhile, the calculated TOF and E-a values are approximately the same over these Pt/CeO2 catalysts pretreated under various calcination conditions, indicating that the RWGS reaction is not affected by the morphologies of anchored Pt nanoparticles or the primary crystallinity of CeO2. TPR and XPS results indicated that the incorporation of Pt promoted the reducibility of CeO2 support and remarkably increased the content of Ce 3 + sites on the catalyst surface. Furthermore, the CO TPSR-MS signal under the condition of pure CO2 flow over Pt/CeO 2 catalyst is far lower than that under the condition of adsorbed CO2 with H-2 -assisted flow, revealing that CO2 molecules adsorbed on Ce3+ active sites have difficult in generating CO directly. Meanwhile, the adsorbed CO2 with the assistance of H-2 can form formate species easily over Ce3+ active sites and then decompose into Ce3+-CO species for CO production, which was identified by in-situ FTIR. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.展开更多
Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffracti...Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffraction(XRD),nitrogen adsorption,temperature-programmed desorption of ammonia(NH3-TPD),and Fourier transform infrared spectroscopy(FT-IR) techniques.The results showed that with the addition of rare earths the BET surface areas,pore volume,the amount of Bronsted acid and the total acidity of catalys...展开更多
Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an en...Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an enhanced activity for the oxygen reduction reaction （ORR） is obtained for the Pt/WO3/C catalyst compared with Pt/C. The higher catalytic activity might be ascribed to the improved Pt dispersion with smaller particle sizes. The Pt/WO3/C catalyst also exhibits a good electrochemical stability under potential cycling. Thus, the Pt/WO3/C catalyst can be used as a potential PEMFC cathode catalyst.展开更多
文摘High-loading Pt/C catalysts play an important role in the fabrication of membrane electrode assemblies with thin catalytic layer,which enhance mass transport and maintain the balance of water and heat.Unfortunately,as the loading increases,the agglomeration and growth of Pt nanoparticles(NPs)occur,causing unsatisfactory performance.Here,we present an efficient method for preparing of highly dispersed and small-sized Pt/C catalysts with Pt loadings varying from 39.01 wt%to 66.48 wt%through the high-temperature shock technique.The high density and ultrafine(~2.5 nm)Pt NPs are successfully anchored onto Vulcan XC-72R carbon black without the use of additional capping agents or surfactants.The modified carbon supports enhance the affinity for Pt precursors,contributing to loading efficiencies of 95%or more,while also providing abundant sites for the nucleation and fixation of Pt NPs,thus preventing agglomeration.In the context of the hydrogen evolution reaction in acidic media,the as-synthesized high-loading Pt/C catalysts show remarkable activity and stability,outperforming the state-of-the-art commercial Pt/C.This is mainly because the combined effects of ultrasmall and uniform Pt NPs,optimized electronic structure of Pt site,superhydrophilicity and effective anchoring of Pt NPs.The polymer electrolyte membrane electrolyzer integrated with Pt60/OX72R and commercial IrO2 reaches 1 A cm^(-2)at 1.77 V and operates stably for 120 hours with a negligible voltage decay.This new strategy is fast,scalable and cost-effective for large-scale production of metal-supported catalysts,especially for the high-loading ones.
文摘It is reported for the first time that the Pt/C catalyst can be prepared with a new and simple organic sol method using SnCl2 as the reductant. It was found that the average size of the Pt particles in the Pt/C catalysts could be controlled with controlling the preparation conditions. The effect of the average sizes of the Pt particles in the Pt/C catalysts obtained with this method on the electrocatalytical activity of the oxidation of methanol was investigated.
基金financial supports from National Key R&D Plan of China (2017YFB0102803)the National Natural Science Foundation of China (21676135)+8 种基金Scientific Instrument Develop Major Project of National Natural Science Foundation of China (51627810)Joint Funds of the National Natural Science Foundation and Liaoning of China (U1508202)Key R&D programs in Jiangsu (BE2018051)“333” project of Jiangsu Province (BRA2018007)Natural Science Foundation of Jiangsu Province (BK20161273, BK20181199)the Graduate Innovation Foundation of Nanjing university (2017ZDL05)support of PAPD of Jiangsu Higher Education Institutions“Six Talent Peaks Program” of Jiangsu ProvinceFundamental Research Funds for the Central Universities, China。
文摘A series of Pt/C catalysts for proton exchange membrane fuel cells(PEMFCs) with various metal loadings is synthesized by a microwave-assisted polyol process via mixing an extremely stable platinum colloid(> 3 months’ shelf life) from single batch preparation with activated carbon ethylene glycol suspension.21 wt%, 42 wt% and 61 wt% Pt loadings are employed to showcase the advantages of the improved polyol process. The ultraviolet(UV)–visible spectra and ζ-potential measurements are conducted to monitor the wet chemistry process during catalyst preparation. The powder X-ray diffraction(XRD), transmission electron microscopy(TEM) and thermogravimetric analysis(TGA) characterizations are carried out on catalysts. The catalyst activities are investigated using electrochemical and single cell tests. The stability of Pt nanoparticle colloid is explored by ORR, cyclic voltammetry(CV) and ζ-potential measurements. The TEM results show the Pt particle sizes of the colloid, and the sizes of the 21 wt%, 42 wt% and 61 wt%Pt/C samples are 2.1–3.9 nm. Because of the high Pt dispersion, the Pt/C catalysts exhibit superior electroactivity toward ORR. In addition, four 61 wt% Pt/C catalysts made from the Pt colloid with 0–3 months’ shelf life show almost the same performance, which exhibits superior stability of the Pt colloid system without surfactant protection.
基金the Natural Science Foundation of China(21922803,92034301,22008066,and 21776077)the China Postdoctoral Science Foundation(BX20190116)+1 种基金the Innovation Program of Shanghai Municipal Education Commission,the Program of Shanghai Academic/Tech-nology Research Leader(21XD1421000)111 Project of the Min-istry of Education of China(B08021)。
文摘Taming the electron transfer across metal–support interfaces appears to be an attractive yet challenging methodology to boost catalytic properties.Herein,we demonstrate a precise engineering strategy for the carbon surface chemistry of Pt/C catalysts—that is,for the electron-withdrawing/donating oxygencontaining groups on the carbon surface—to fine-tune the electrons of the supported metal nanoparticles.Taking the ammonia borane hydrolysis as an example,a combination of density functional theory(DFT)calculations,advanced characterizations,and kinetics and isotopic analyses reveals quantifiable relationships among the carbon surface chemistry,Pt charge state and binding energy,activation entropy/enthalpy,and resultant catalytic activity.After decoupling the influences of other factors,the Pt charge is unprecedentedly identified as an experimentally measurable descriptor of the Pt active site,contributing to a 15-fold increment in the hydrogen generation rate.Further incorporating the Pt charge with the number of Pt active sites,a mesokinetics model is proposed for the first time that can individually quantify the contributions of the electronic and geometric properties to precisely predict the catalytic performance.Our results demonstrate a potentially groundbreaking methodology to design and manipulate metal–carbon catalysts with desirable properties.
文摘Supported metal catalysts are the backbone of heterogeneous catalysis,playing a crucial role in the modern chemical industry.Metal-support interactions(MSIs)are known important in determining the catalytic performance of supported metal catalysts.This is particularly true for single-atom catalysts(SACs)and pseudo-single-atom catalysts(pseudo-SACs),where all metal atoms are dispersed on,and interact directly with the support.Consequently,the MSI of SACs and pseudo-SACs are theoretically more sensitive to modulation compared to that of traditional nanoparticle catalysts.In this work,we experimentally demonstrated this hypothesis by an observed size-dependent MSI modulation.We fabricated CoFe_(2)O_(4) supported Pt pseudo-SACs and nanoparticle catalysts,followed by a straightforward water treatment process.It was found that the covalent strong metal-support interaction(CMSI)in pseudo-SACs can be weakened,leading to a significant activity improvement in methane combustion reaction.This finding aligns with our recent observation of CoFe_(2)O_(4) supported Pt SACs.By contrast,the MSI in Pt nanoparticle catalyst was barely affected by the water treatment,giving rise to almost unchanged catalytic performance.This work highlights the critical role of metal size in determining the MSI modulation,offering a novel strategy for tuning the catalytic performance of SACs and pseudo-SACs by fine-tuning their MSIs.
文摘The efficient conversion of lignin into mono-cycloalkanes via both C–O and C–C bonds cleavage are attractive,but challenging due to the high C–C bond dissociation energy.Previous studies have demonstrated that NbO_(x)-based catalysts exhibited exceptional capabilities for C_(Ar)–C bond cleavage and broken the limitation of lignin monomers.In this work,we presented an economical multifunctional Pt-Nb/MOR catalyst that achieved an impressive monomer yield of 147%during the depolymerization and hydrodeoxygenation of lignin into mono-cycloalkanes.Reaction pathway studies showed that unlike traditional NbO_(x)-based catalytic system,bicyclohexane was an important intermediate in this system and followed the C_(sp3)–C_(sp3)cleavage pathway after complete cyclic-hydrogenation.Deep investigations demonstrated that the doping of Nb in Pt/MOR not only enhanced the activation of hydrogen by Pt,but also increased the acidity of MOR,both of these are favor for the hydrogenolytic cleavage of C_(sp3)–C_(sp3)bonds.This work provides a low-cost catalyst to obtain high-yield monomers from lignin under relatively mild conditions and would help to design catalysts with higher activity for the valorization of lignin.
基金Project(50573041)supported by the National Natural Science Foundation of China
文摘Platinum nanoparticles supported on carbons（Pt/C,60%,mass fraction） electrocatalysts for direct methanol fuel cell（DMFC） were prepared by citrate-stabilized method with different reductants and carbon supports.The catalysts were characterized by X-ray diffraction（XRD）,transmission electron microscopy（TEM） and cyclic voltammetry（CV）.It is found that the size of Pt nanoparticles on carbon is controllable by citrate addition and reductant optimization,and the form of carbon support has a great influence on electrocatalytic activity of catalysts.The citrate-stabilized Pt nanoparticles supported on BP2000 carbon,which was reduced by formaldehyde,exhibit the best performance with about 2 nm in diameter and 66.46 m2/g（Pt） in electrocatalytic active surface（EAS） area.Test on single DMFC with 60%（mass fraction） Pt/BP2000 as cathode electrocatalyst showed maximum power density at 78.8 mW/cm2.
基金supported by the Jiangsu Planned Projects for Postdoctoral Research Funds(1301080C)NNSFC(21202141,21173182)+1 种基金Key Science&Technology Specific Projects of Yangzhou(YZ20122029)the Innovation Foundation of Yangzhou University(2015CXJ009)~~
文摘The structure and catalytic properties of PtSn catalysts supported on SUZ-4 and ZSM-5 zeolite have been studied by using various experimental techniques including XRD,nitrogen adsorption,NH3-TPD,TG,H2-TPR and TPO techniques combined with propane dehydrogenation tests.It has been shown that SUZ-4-supported PtSnNa（PtSnNa/SUZ-4） was determined to be a better catalyst for propane dehydrogenation than conventional catalysts supported on ZSM-5,owing to its higher catalytic activity and stability.Dibenzothiophene poisoning experiments were performed to investigate the detailed structures of the two supported catalysts.The characterization of the two catalysts indicates that the distribution of Pt on the porous support affects the activity.In contrast to ZSM-5-supported catalysts,Pt particles on the PtSnNa/SUZ-4 are primarily dispersed over the external surface and are not as readily deactivated by carbon deposition.This is because that the strong acid sites of the SUZ-4 zeolite evidently prevented the impregnation of the Pt precursor H_2PtCl_6 into the zeolite.In contrast,the weak acid sites of the ZSM-5 zeolite led to more of the precursor entering the zeolite tunnels,followed by transformation to highly dispersed Pt clusters during calcination.In the case of the PtSnNa/ZSM-5,the interactions between Sn oxides and the support were lessened,owing to the weaker acidity of the ZSM-5 zeolite.The dispersed Sn oxides were therefore easier to reduce to the metallic state,thus decreasing the catalytic activity for hydrocarbon dehydrogenation.
基金supported by the National Natural Science Foundation of China(21506194,21676255)the Provincial Natural Science Foundation of Zhejiang Province(LY16B070011)the Commission of Science and Technology of Zhejiang Province(2017C33106,2017C03007)~~
文摘Platinum/cerium-zirconium-sulfate（Pt/Ce-Zr-SO_4^（2-）） catalysts were prepared by wetness impregnation.Catalytic activities were evaluated from the combustion of propene and CO.Sulfate（SO_4^（2-））addition improved the catalytic activity significantly.When using Pt/Ce-Zr-SO_4^（2-） with 10 wt%SO_4^（2-）,the temperature for 90%conversion of propene and CO decreased by 75℃ compared with Pt/Ce-Zr.The conversion exceeded 95%at 240℃ even after 0.02%sulfur dioxide poisoning for 20 h.Temperature-programmed desorption of CO and X-ray photoelectron spectroscopy analyses revealed an improvement in Pt dispersion onto the Ce-Zr-SO_4^（2-） support,and the increased number of Pt particles built up more Pt^（-）-（SO_4^（2-））^（-） couples,which resulted in excellent activity.The increased total acidity and new Bronsted acid sites on the surface provided the Pt/Ce-Zr-SO_4^（2-） with good sulfur resistance.
基金This work is supported by the National Natural Science Foundation of China （No.51372248, No.51432009 and No.51502297）, Instrument Developing Project of the Chinese Academy of Sciences （No.yz201421）, the CAS/SAFEA International Partnership Program for Creative Research Teams of Chinese Academy of Sciences, China.
文摘A variety of spherical and structured activated charcoal supported Pt/Fe3O4 composites with an average particle size of ~100 nm have been synthesized by a self-assembly method using the difference of reduction potential between Pt （Ⅳ） and Fe （Ⅱ） precursors as driving force. The formed Fe3O4 nanoparticles （NPs） effectively prevent the aggregation of Pt nanocrystallites and promote the dispersion of Pt NPs on the surface of catalyst, which will be favorable for the exposure of Pt active sites for high-efficient adsorption and contact of substrate and hydrogen donor. The electron-enrichment state of Pt NPs donated by Fe304 nanocrystallites is corroborated by XPS measurement, which is responsible for promoting and activating the terminal C=O bond of adsorbed substrate via a vertical configuration. The experimental results show that the activated charcoal supported Pt/Fe3O4 catalyst exhibits 94.8% selectivity towards cinnamyl alcohol by the transfer hydrogenation of einnamaldehyde with Pt loading of 2.46% under the optimum conditions of 120 ℃ for 6 h, and 2-propanol as a hydrogen donor. Additionally, the present study demonstrates that a high-efficient and recyclable catalyst can be rapidly separated from the mixture due to its natural magnetism upon the application of magnetic field.
基金The Department of Science and Technology of Henan Province (No. 0324210007)
文摘In this paper, MPt/C (M= La, Nd) catalysts of PEMFC were synthesized by microwave radiation process. The crystallinity and structure of catalysts were respectively analyzed by XRD and nitrogen adsorption tests. The activity of catalysts was investigated by electrochemistry experiment. The results showed that: 1) compared with Pt/C catalyst prepared by typical impregnation-reduction process, the size of MPt/C catalyst particle decreased and the available crystal for O2 reduction increased; 2) the MPt/C catalysts had relatively high BET surface areas; and 3)these crystal transformations of the MPt/C catalyst brought high the electrocatalytic activity, and as a result, improved the power of PEMFC.
基金financially supported by the National Natural Science Foundation of China(21173195)~~
文摘A series of K-promoted Pt/Al2O3 catalysts were tested for CO oxidation. It was found that the addition of K significantly enhanced the activity. A detailed kinetic study showed that the activation energies of the K-containing catalysts were lower than those of the K-free ones, particularly for catalysts with high Pt contents （51.6 k）/mol for 0.42K-2.0Pt/Al2O3 and 6：3.6 kJ/mol for 2.0Pt/Al2O3 ）. The CO reaction orders were higher for the K-containing catalysts （about -0.2） than for the K-free ones （about -0.5）, with the former having much lower equilibrium constants for CO adsorption than the latter. In situ Fourier-transform infrared spectroscopy showed that surface CO desorption from the 0.42K-2.0Pt/Al2O3 catalyst was easier than from 2.0Pt/Al2O3. The promoting effect of K was therefore caused by weakening of the interactions between CO and surface Pt atoms. This decreased coverage of the catalyst with CO and facilitated competitive O2 chemisorption on the Pt surface, and significantly lowered the reaction barrier between chemisorbed CO and O2 species.
基金Project supported by the National Natural Science Foundation of China(21506194,21676255)the Natural Science Foundation of Zhejiang Province(Y16B070011)the Commission of Science and Technology of Zhejiang Province(2017C03007,2017C33106)
文摘The metal oxides CuMnCe and CeY washcoats on cordierite were prepared using an impregnation method, and then used as support for the active Pt component to prepare the Pt/CuMnCe and Pt/CeY monolithic catalysts for the deep oxidation of VOCs. In comparison with the Pt/CeY, CuMnCe, and CeY monolithic catalysts, the Pt/CuMnCe monolithic catalyst shows an excellent performance for toluene,ethyl acetate,and n-hexane oxidation and the Tis low to 216, 200 and 260 ℃,respectively. The active components Pt/PtO and CuMnCe result in a better synergetic interaction, which promote the catalyst reducibility, increase the oxygen mobility, and enhance the adsorption and activation of organic molecules.
基金National Natural Science Foundation of China (nos.21476226 and 21506204)National Key Projects for Fundamental Research and Development of China (2016YFB0600902)+1 种基金the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020400)the Youth Innovation Promotion Association CAS for financial support
文摘Reverse water gas shift (RWGS) reaction can serve as a pivotal stage in the CO2 conversion processes, which is vital for the utilization of CO2. In this study, RWGS reaction was performed over Pt/CeO2 catalysts at the temperature range of 200-500 degrees C under ambient pressure. Compared with pure CeO2, Pt/CeO2 catalysts exhibited superior RWGS activity at lower reaction temperature. Meanwhile, the calculated TOF and E-a values are approximately the same over these Pt/CeO2 catalysts pretreated under various calcination conditions, indicating that the RWGS reaction is not affected by the morphologies of anchored Pt nanoparticles or the primary crystallinity of CeO2. TPR and XPS results indicated that the incorporation of Pt promoted the reducibility of CeO2 support and remarkably increased the content of Ce 3 + sites on the catalyst surface. Furthermore, the CO TPSR-MS signal under the condition of pure CO2 flow over Pt/CeO 2 catalyst is far lower than that under the condition of adsorbed CO2 with H-2 -assisted flow, revealing that CO2 molecules adsorbed on Ce3+ active sites have difficult in generating CO directly. Meanwhile, the adsorbed CO2 with the assistance of H-2 can form formate species easily over Ce3+ active sites and then decompose into Ce3+-CO species for CO production, which was identified by in-situ FTIR. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B. V. and Science Press. All rights reserved.
基金supported by the Foundation of Jiangsu Key Laboratory of Precious Metals Chemistry (SYGK0710)Natural Scientific Foundation of Jiangsu Teachers University of Technology (KYY06029)
文摘Monometallic catalyst Pt/SAPO-11 was prepared by impregnation method.Bimetallic catalysts LaPt/SAPO-11 or CePt/SAPO-11 was prepared by sequential impregnation method.The catalysts were characterized by X-ray diffraction(XRD),nitrogen adsorption,temperature-programmed desorption of ammonia(NH3-TPD),and Fourier transform infrared spectroscopy(FT-IR) techniques.The results showed that with the addition of rare earths the BET surface areas,pore volume,the amount of Bronsted acid and the total acidity of catalys...
基金financially supported by the National Natural Science Fundation of China(No.51125007)the National Basic Research Program(No.2012CB215500)
文摘Pt/WO3/C nanocomposites with parallel WO3 nanorods were synthesized and applied as the cathode catalyst for proton exchange membrane fuel cells （PEMFCs）. Electrochemical results and single cell tests show that an enhanced activity for the oxygen reduction reaction （ORR） is obtained for the Pt/WO3/C catalyst compared with Pt/C. The higher catalytic activity might be ascribed to the improved Pt dispersion with smaller particle sizes. The Pt/WO3/C catalyst also exhibits a good electrochemical stability under potential cycling. Thus, the Pt/WO3/C catalyst can be used as a potential PEMFC cathode catalyst.
