Al2O3 and Ce-Zr mixed oxides are important components of the automobile three-way catalyst.Various contents modifying A12O3(GAL) was physically introduced into Ce-Zr-Al mixed oxides(CZA) to form series of GAL/CZA comp...Al2O3 and Ce-Zr mixed oxides are important components of the automobile three-way catalyst.Various contents modifying A12O3(GAL) was physically introduced into Ce-Zr-Al mixed oxides(CZA) to form series of GAL/CZA composition.The Pd/Rh catalyst samples were prepared by different GAL/CZA support loading Pd/Rh,then aged at 950 oC for 6 h.The catalytic behavior of different Pd/Rh catalyst samples was studied.Surface area,oxygen storage capacity(OSC) and H2 adsorption capacity(TPR) of fresh and aged samples were...展开更多
A vacuum heating operation at 623 K on the surfaces of SiO_2-supported promoted ca- talysts makes it possible to reveal the electron transfer from Co and Fe additives to Rh atoms: a Rh catalyst containing 1 % Eh under...A vacuum heating operation at 623 K on the surfaces of SiO_2-supported promoted ca- talysts makes it possible to reveal the electron transfer from Co and Fe additives to Rh atoms: a Rh catalyst containing 1 % Eh under CO exhibits geminal CO IR bands only, while the presence of Co and Fe in promoted Rh catalysts results in linear and bridged CO chemisorp- tions on Rh in connection with their promotion in the selective hydroformylation of propy- lene.展开更多
A chiral catalyst, Cp＊RhTsDPEN （Cp＊ = pentamethyl cyclopentadiene, TsDPEN = substitutive phenylsulfonyl-l,2-diphenylethylenediamine）, was synthesized and immobilized at the surface of glass. The immobilized cataly...A chiral catalyst, Cp＊RhTsDPEN （Cp＊ = pentamethyl cyclopentadiene, TsDPEN = substitutive phenylsulfonyl-l,2-diphenylethylenediamine）, was synthesized and immobilized at the surface of glass. The immobilized catalyst exhibited good catalytic efficiency for asymmetric transfer hydrogenation of aromatic ketones in water with HCOONa as hydrogen source.展开更多
A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst...A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst under similar reaction condition. The difference between the activity of above two catalyst systems is clearly caused by the intrinsic properties generated by the introduction of Nd.展开更多
By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts d...By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.展开更多
The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) ...The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.展开更多
The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability...The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.展开更多
Metal oxide-promoted Rh-based catalysts have been widely used for CO2hydrogenation,especially for the ethanol synthesis.However,this reaction usually suffers low CO2conversion and alcohols selectivity due to the forma...Metal oxide-promoted Rh-based catalysts have been widely used for CO2hydrogenation,especially for the ethanol synthesis.However,this reaction usually suffers low CO2conversion and alcohols selectivity due to the formation of byproducts methane and CO.This paper describes an efficient vanadium oxide promoted Rh-based catalysts confined in mesopore MCM-41.The Rh-0.3VOx/MCM-41 catalyst shows superior conversion（～12%）and ethanol selectivity（～24%）for CO2hydrogenation.The promoting effect can be attributed to the synergism of high Rh dispersion by the confinement effect of MCM-41 and the formation of VOx-Rh interface sites.Experimental and theoretical results indicate the formation of til-CO at VOx-Rh interface sites is easily dissociated into*CHx,and then*CHxcan be inserted by CO to form CH3CO*,followed by CH3CO*hydrogenation to ethanol.展开更多
Rh single atom catalysts(SACs)have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the develo...Rh single atom catalysts(SACs)have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the development and application of Rh SACs,there are few reports on the precise control of the local coordination environment of Rh single sites on CeO_(2) and their catalytic performance for N_(2)O decomposition.Herein,Rh/CeO_(2) catalysts with different Rh-O coordination numbers(CNs)were successfully prepared using different CeO_(2) supports and a simple incipient wetness impregnation(IWI)method.It is observed that the Rh/CeO_(2) catalyst with slightly higher CN of Rh-O(Rh/CeO_(2)-H)prepared from CeO_(2) shows much higher N_(2)O decomposition activity than the catalyst with lower CN of Rh-O(Rh/CeO_(2)-L)obtained from Ce(OH)_(x).The Rh species within Rh/CeO_(2)-H are found to be more reactive than those within Rh/CeO_(2)-L,which can better facilitate the O_(2)desorption once formed during N_(2)O deco mposition.In additio n,more surface oxygen vacancies are present on Rh/CeO_(2)-H than on Rh/CeO_(2)-L,well explaining the superior N_(2)O adsorption and activation capability on the former catalyst.It is concluded that more abundant oxygen vacancies and reactive Rh single atom sites with slightly higher CN of Rh-O and significantly higher reducibility altogether contribute to the superior N_(2)O decomposition activity on the Rh/CeO_(2)-H catalyst.展开更多
Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. ...Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. The adsorbed hydrogen atoms were transferred to SiO2 surface by ＂spill-over＂ and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO2 catalyst using in-situ FT-IR. It was found that CO2 was formed before CO could be detected when CH4 and O2 were introduced over the preoxidized Rh/SiO2 catalyst, whereas CO was detected before CO2 was formed over the prereduced Rh/SiO2 catalyst.展开更多
The 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction （UAMR） co-precipitation, UAMR separation precipitation, co-impregnation, an...The 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction （UAMR） co-precipitation, UAMR separation precipitation, co-impregnation, and sequential impregnation. The catalysts were physico-chemically characterized by N2 adsorption, XRD, TEM, and Hz-TPR techniques, and evaluated for three-way catalytic activities with simulated automobile exhaust. UAMR co-precipitation- and UAMR separation precipitation- prepared catalysts exhibited a high surface area and metal dispersion, wide λ window and excellent conversion for NOx reduction under lean conditions. Both fresh and aged catalysts from UAMR- precipitation showed the high surface areas of ca. 60-67 m^2/g and 18-22 m^2/g, respectively, high metal dispersion of 41%-55%, and small active particle diameters of 2.1-2.7 nm. When these catalysts were aged, the catalysts prepared by the UAMR method exhibited a wider working window （△λ = 0.284--0.287） than impregnated ones （△λ = 0.065-0.115） as well as excellent three-way catalytic performance, and showed lower/so （169℃） and T90 （195℃） for NO reduction than the aged catalysts from impregnation processes, which were at 265 and 309℃, respectively. This implied that the UAMR-separation precipitation has important potential for industrial applications to improve catalytic performance and thermal stability. The fresh and aged 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts prepared by the UAMR-separation precipitation method exhibited better catalytic performance than the corresponding catalysts prepared by conventional impregnation routes.展开更多
The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were ...The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were obtained. The activation energy. H_2 and CO dependenceorders for ethanol and acetaldehyde formation differed greatly, the large difference seemed to implythat they were formed through different intermediates.展开更多
Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has be...Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has become an irreplaceablecomponent of three-way catalysts due to its superior NOx elimination,high N2selectivity,and simultaneous elimination of CO and hydrocarbons.In this review,we systematically review the recent development of Rh-based three-way catalystsin terms of potential supports and effective active center construction strategies.We further summarize the key role of Rh metal in the three-way catalytic mechanismand reaction kinetics.Finally,we conclude the current challenges and futureopportunities facing Rh-based catalysts.It is believed that based on the deep understandingof Rh-based three-way catalysts,the design of Rh-based catalysts withgood low-temperature catalytic performance and low cost is expected to be realizedin the future.展开更多
A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7...A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.展开更多
A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic ...A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.展开更多
In this paper,a series of Rh/CeO_(2) catalysts with three-dimensional porous nanorod frameworks and large specific surface area were prepared by chemical dealloying Al–Ce–Rh precursor alloys and then calcining in pu...In this paper,a series of Rh/CeO_(2) catalysts with three-dimensional porous nanorod frameworks and large specific surface area were prepared by chemical dealloying Al–Ce–Rh precursor alloys and then calcining in pure O_(2).The effects of the Rh content and calcination temperature on CO oxidation and CH_(4) combustion were studied,and the results reveal that the Rh/CeO_(2) catalysts produced by dealloying melt-spun Al_(91.3)Ce_(8)Rh_(0.7) alloy ribbons and then calcining at 500℃ exhibit the best catalytic activity,the reaction temperatures for the complete conversion of CO and CH_(4) are as low as 90 and 400℃,respectively.Furthermore,after 150 h of continuous testing at high concentrations of H2O and CO_(2),the nature of the catalyst is not irreversibly destroyed and can still return to its initial level of activity.This excellent catalytic activity is attributed to a portion of Rh being uniformly distributed on the CeO_(2) nanorod surface in the form of nanoparticles,forming strong Rh–CeO_(2) interfacial synergy.Another portion of Rh permeated into the CeO_(2) lattice,which results in a significant increase in the number of oxygen vacancies in CeO_(2),thus allowing more surface active oxygen to be adsorbed and converted from the gas phase.Moreover,the catalytic reaction can proceed even in an oxygen-free environment due to the excellent oxygen storage performance of the Rh/CeO_(2) catalyst.展开更多
The three-way catalyst(TWC),as a promising approach to control automobile exhaust emission,has been widely studied and applied.However,it still suffers from the high light-off temperature and poor stability.Herein,we ...The three-way catalyst(TWC),as a promising approach to control automobile exhaust emission,has been widely studied and applied.However,it still suffers from the high light-off temperature and poor stability.Herein,we synthesized a multicomponent catalyst Rh/Cu-CeSn by using Cu metal doping to modify the Ce-based solid solution,which exhibited good TWC catalytic performance:the light-off temperatures for CO,NO,and C_(3)H_(6)conversion are 172℃,266℃,and 193℃,respectively.Moreover,the catalyst still maintained good activity after 12 h of the continuous reaction under high-temperature conditions.The experiments and mechanism studies reveal that due to the redox pair Cu^(+)/Cu^(2+),the Cu incorporation can effectively inhibit the Rh transition to the oxidation state and greatly enhance the catalytic activity and stability.This work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of noble metal-based catalysts,which significantly reduces environmental pollution from energy applications.展开更多
基金supported by the National High Technology Research and Development Program (863) of China (2006AA03Z462)
文摘Al2O3 and Ce-Zr mixed oxides are important components of the automobile three-way catalyst.Various contents modifying A12O3(GAL) was physically introduced into Ce-Zr-Al mixed oxides(CZA) to form series of GAL/CZA composition.The Pd/Rh catalyst samples were prepared by different GAL/CZA support loading Pd/Rh,then aged at 950 oC for 6 h.The catalytic behavior of different Pd/Rh catalyst samples was studied.Surface area,oxygen storage capacity(OSC) and H2 adsorption capacity(TPR) of fresh and aged samples were...
文摘A vacuum heating operation at 623 K on the surfaces of SiO_2-supported promoted ca- talysts makes it possible to reveal the electron transfer from Co and Fe additives to Rh atoms: a Rh catalyst containing 1 % Eh under CO exhibits geminal CO IR bands only, while the presence of Co and Fe in promoted Rh catalysts results in linear and bridged CO chemisorp- tions on Rh in connection with their promotion in the selective hydroformylation of propy- lene.
基金the Shanghai Sciences and Technologies Development Fund(Nos.13ZR1458700 and 12nm0500500)the Shanghai Municipal Education Commission(Nos.14YZ074,12ZZ135)Shanghai Normal University(Nos.DXL122,SK201329)for financial support
文摘A chiral catalyst, Cp＊RhTsDPEN （Cp＊ = pentamethyl cyclopentadiene, TsDPEN = substitutive phenylsulfonyl-l,2-diphenylethylenediamine）, was synthesized and immobilized at the surface of glass. The immobilized catalyst exhibited good catalytic efficiency for asymmetric transfer hydrogenation of aromatic ketones in water with HCOONa as hydrogen source.
文摘A Nd promoted-Rh catalysts supported on polymer-derived carbon beads for vapor-phase methanol carbonylation was developed. Rh-Nd bimetallic catalysts obviously have higher activity than that of supported Rh catalyst under similar reaction condition. The difference between the activity of above two catalyst systems is clearly caused by the intrinsic properties generated by the introduction of Nd.
基金supported by the Petrochemical Research Institute Foundation(21-CB-09-01)the National Natural Science Foundation of China(22302186,22025205)+1 种基金the China Postdoctoral Science Foundation(2022M713030,2023T160618)the Fundamental Research Funds for the Central Universities(WK2060000058,WK2060000038).
文摘By simplifying catalyst-product separation and reducing phosphorus waste,heterogeneous hydroformylation offers a more sustainable alternative to homogeneous processes.However,heterogeneous hydroformylation catalysts developed thus far still suffer from the issues of much lower activity and metal leaching,which severely hinder their practical application.Here,we demonstrate that incorporating phosphorus(P)atoms into graphitic carbon nitride(PCN)supports facilitates charge transfer from Rh to the PCN support,thus largely enhancing electronic metal-support interactions(EMSIs).In the styrene hydroformylation reaction,the activity of Rh_(1)/PCN single-atom catalysts(SACs)with varying P contents exhibited a volcano-shaped relationship with P doping,where the Rh_(1)/PCN SAC with optimal P doping showed exceptional activity,approximately 5.8-and 3.3-fold greater than that of the Rh_(1)/g-C_(3)N_(4)SAC without P doping and the industrial homogeneous catalyst HRh(CO)(PPh_(3))_(3),respectively.In addition,the optimal Rh_(1)/PCN SAC catalyst also demonstrated largely enhanced multicycle stability without any visible metal aggregation owing to the increased EMSIs,which sharply differed from the severe metal aggregation of large nanoparticles on the Rh_(1)/g-C_(3)N_(4)SAC.Mechan-istic studies revealed that the enhanced catalytic performance could be attributed to electron-deficient Rh species,which reduced CO adsorption while simultaneously promoting alkene adsorption through increased EMSIs.These findings suggest that tuning EMSIs is an effective way to achieve SACs with high activity and durability.
基金Project supported by the National Key Research and Development Program(2017YFC0211003)GM Global Research and Development(GAC 2696)。
文摘The activity and hydrothermal stability of the Rh/Ce_(x)Zr_(1-x)O_(2)(x=0,0.05,0.3,0.5) model three-way catalysts for gasoline vehicle emissions control were investigated in this work.Among the Rh/Ce_(x)Zr_(1-x)O_(2) samples with different Ce/Zr ratios,the Rh/ZrO_(2) sample exhibits a significantly better activity and hydrothermal stability than the rest of the samples.The impacts of having more Ce components in the Rh/Ce_(x)Zr_(1-x)O_(2) catalysts are associated with the strong Rh-O-Ce interaction that tends to over stabilize the rhodium species.A significant amount of such rhodium atoms can be found in the bulk of the support oxides after a hydrothermal aging at 1050℃ with 10% H_(2)O in air for 12 h.Differently,the sintering of rhodium on the surface of Rh/ZrO_(2) catalysts is the main reason for the catalyst deactivation during the hydrothermal aging.These findings provide an example where high dispersion of supported metal induced by strong metal-support interactions does not necessarily lead to high catalytic activity.
基金Project supported by Yunnan Province Science Technology Program (2002C001Z) the National High Technology Research and Development Program ( 863 ) of China ( 2002AA321060 ) Yunnan Province Science Technology Program (2004B0028Q)
文摘The catalysts with Rh loading on different cerium-zirconium mixed oxides were characterized by BET, H2-TPR and OSC. The effects of different cerium-zirconium mixed oxides on catalytic performance and thermal stability of Rh loaded catalyst were studied. The results show that: (1) Rh can enhance cerium-zirconium mixed oxides OSC and catalytic reaction rates; (2) cerium-zirconium mixed oxides with high Ce contents and low Zr contents are more favorable to the stability of catalysts. Moreover, the contents of CeO2 have important effect on catalysts characteristics, and the addition of some rare earth components, such as La, Pr and Nd also have some influences.
基金supported by the National Key R&D Program of China (2016YFB0600901)the National Natural Science Foundation of China (21525626, 21603159, 21676181)the Program of Introducing Talents of Discipline to Universities (B06006)
文摘Metal oxide-promoted Rh-based catalysts have been widely used for CO2hydrogenation,especially for the ethanol synthesis.However,this reaction usually suffers low CO2conversion and alcohols selectivity due to the formation of byproducts methane and CO.This paper describes an efficient vanadium oxide promoted Rh-based catalysts confined in mesopore MCM-41.The Rh-0.3VOx/MCM-41 catalyst shows superior conversion（～12%）and ethanol selectivity（～24%）for CO2hydrogenation.The promoting effect can be attributed to the synergism of high Rh dispersion by the confinement effect of MCM-41 and the formation of VOx-Rh interface sites.Experimental and theoretical results indicate the formation of til-CO at VOx-Rh interface sites is easily dissociated into*CHx,and then*CHxcan be inserted by CO to form CH3CO*,followed by CH3CO*hydrogenation to ethanol.
基金Project supported by the Startup Fund(F.L.)from the University of Central Florida(UCF)National Science Foundation grants(CHE-1955343,DMR-1920050).
文摘Rh single atom catalysts(SACs)have been insensitively investigated recently due to the maximum utilization efficiency of Rh,one of the most expensive precious metals.Although great efforts have been made in the development and application of Rh SACs,there are few reports on the precise control of the local coordination environment of Rh single sites on CeO_(2) and their catalytic performance for N_(2)O decomposition.Herein,Rh/CeO_(2) catalysts with different Rh-O coordination numbers(CNs)were successfully prepared using different CeO_(2) supports and a simple incipient wetness impregnation(IWI)method.It is observed that the Rh/CeO_(2) catalyst with slightly higher CN of Rh-O(Rh/CeO_(2)-H)prepared from CeO_(2) shows much higher N_(2)O decomposition activity than the catalyst with lower CN of Rh-O(Rh/CeO_(2)-L)obtained from Ce(OH)_(x).The Rh species within Rh/CeO_(2)-H are found to be more reactive than those within Rh/CeO_(2)-L,which can better facilitate the O_(2)desorption once formed during N_(2)O deco mposition.In additio n,more surface oxygen vacancies are present on Rh/CeO_(2)-H than on Rh/CeO_(2)-L,well explaining the superior N_(2)O adsorption and activation capability on the former catalyst.It is concluded that more abundant oxygen vacancies and reactive Rh single atom sites with slightly higher CN of Rh-O and significantly higher reducibility altogether contribute to the superior N_(2)O decomposition activity on the Rh/CeO_(2)-H catalyst.
基金This study was supported by the grant of 2004C31053 from the Ministry of Science and Technology of Zhejiang Province, China, and the grant of Y404305 from the Natural Science Foundation of Zhejiang Province, Chinathe grant of 20673101, 20673102 from National Natural Science Foundation of China.
文摘Partial oxidation of methane to syngas （POM） over Rh/SiO2 catalyst was investigated using in-situ FT-IR. When methane interacted with 1.0wt%Rh/SiO2 catalyst, it was dissociated to adsorbed hydrogen and CHx species. The adsorbed hydrogen atoms were transferred to SiO2 surface by ＂spill-over＂ and reacted with lattice oxygen to form surface -OH species. POM mechanism was investigated over Rh/SiO2 catalyst using in-situ FT-IR. It was found that CO2 was formed before CO could be detected when CH4 and O2 were introduced over the preoxidized Rh/SiO2 catalyst, whereas CO was detected before CO2 was formed over the prereduced Rh/SiO2 catalyst.
基金supported by the National Nature Foundation of China(No.21277009)the Beijing National Nature Foundation(No.2101002)+2 种基金the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality(No.PHR201107104,PHR200907105)the National Research and Development Program(863)of China(No.2011AA03A406)the National Industrial Project of New Rare Earth Materials
文摘The 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts were fabricated via different methods, including ultrasonic-assisted membrane reduction （UAMR） co-precipitation, UAMR separation precipitation, co-impregnation, and sequential impregnation. The catalysts were physico-chemically characterized by N2 adsorption, XRD, TEM, and Hz-TPR techniques, and evaluated for three-way catalytic activities with simulated automobile exhaust. UAMR co-precipitation- and UAMR separation precipitation- prepared catalysts exhibited a high surface area and metal dispersion, wide λ window and excellent conversion for NOx reduction under lean conditions. Both fresh and aged catalysts from UAMR- precipitation showed the high surface areas of ca. 60-67 m^2/g and 18-22 m^2/g, respectively, high metal dispersion of 41%-55%, and small active particle diameters of 2.1-2.7 nm. When these catalysts were aged, the catalysts prepared by the UAMR method exhibited a wider working window （△λ = 0.284--0.287） than impregnated ones （△λ = 0.065-0.115） as well as excellent three-way catalytic performance, and showed lower/so （169℃） and T90 （195℃） for NO reduction than the aged catalysts from impregnation processes, which were at 265 and 309℃, respectively. This implied that the UAMR-separation precipitation has important potential for industrial applications to improve catalytic performance and thermal stability. The fresh and aged 0.7 wt% Pt ＋ 0.3 wt% Rh/Ce0.6Zr0.4O2 catalysts prepared by the UAMR-separation precipitation method exhibited better catalytic performance than the corresponding catalysts prepared by conventional impregnation routes.
基金This work was financially by the Chinese Science and Technology Ministry (Grant No.G1999022404)
文摘The kinetics of CO hydrogenation for the synthesis of C_2 oxygenates overRh-Mn-Li-Fe/SiO_2 was investigated. Kinetic parameters for the formation of ethanol, acetaldehyde,C'2 oxygenates, methanol and methane were obtained. The activation energy. H_2 and CO dependenceorders for ethanol and acetaldehyde formation differed greatly, the large difference seemed to implythat they were formed through different intermediates.
基金supported by the financial aid from National Science and Technology Major Project of China(2021YFB3500700)National Natural Science Foundation of China(22020102003,22025506,22271274 and U23A20140)Program of Science and Technology Development Plan of Jilin Province of China(20230101035JC and 20230101022JC).
文摘Three-way catalysts are widely used to control criterion pollutant emissions fromthe increasing gasoline engines.With the stringent requirements of automotivepollutant emission standards in various countries,Rh has become an irreplaceablecomponent of three-way catalysts due to its superior NOx elimination,high N2selectivity,and simultaneous elimination of CO and hydrocarbons.In this review,we systematically review the recent development of Rh-based three-way catalystsin terms of potential supports and effective active center construction strategies.We further summarize the key role of Rh metal in the three-way catalytic mechanismand reaction kinetics.Finally,we conclude the current challenges and futureopportunities facing Rh-based catalysts.It is believed that based on the deep understandingof Rh-based three-way catalysts,the design of Rh-based catalysts withgood low-temperature catalytic performance and low cost is expected to be realizedin the future.
基金supportd by the NNSF of China(#29773037)the NSF of Fujian province(#E9910001 and#E0010006).|
文摘A new catalyst for methanol synthesis, ZnO-promoted rhodium supported on carbon nanotubes, was developed. It was found that the Rh-ZnO/CNTs catalyst had high activity of 411.4 mg CH3OH/g/cat/h and selectivity of 96.7 % for methanol at 1 MPa and 523 K. The activity of this catalyst is much higher than that of NC 207 catalyst at the same reaction conditions. It was suggested that the multi-walled structure CNTs favored both the couple transfer of the proton and electron over the surface of the catalyst and the uptake of hydrogen which was favorable to methanol synthesis.
文摘A novel TPPTS-Rh/SiO2 catalyst, prepared by directly modifying a heterogeneous high-surface-area Rh/SiO2 catalyst with water-soluble TPPTS ligands, could decrease the resistance of mass transfer in water/oil biphasic media for the hydroformylation of higher olefins. The catalytic performance for hydroformylation on this biphasic TPPTS-Rh/SiO2 catalyst system was higher than those of the traditional biphasic HRhCO(TPPTS)3 systems, owing to the chemical bonds between the highly dispersed Rh metal particles and the TPPTS ligands. The catalyst system is applicable for hydroformylation of higher olefins such as 1-dodecene.
基金Project supported by the National Natural Science Foundation of China (51771141,51671155)。
文摘In this paper,a series of Rh/CeO_(2) catalysts with three-dimensional porous nanorod frameworks and large specific surface area were prepared by chemical dealloying Al–Ce–Rh precursor alloys and then calcining in pure O_(2).The effects of the Rh content and calcination temperature on CO oxidation and CH_(4) combustion were studied,and the results reveal that the Rh/CeO_(2) catalysts produced by dealloying melt-spun Al_(91.3)Ce_(8)Rh_(0.7) alloy ribbons and then calcining at 500℃ exhibit the best catalytic activity,the reaction temperatures for the complete conversion of CO and CH_(4) are as low as 90 and 400℃,respectively.Furthermore,after 150 h of continuous testing at high concentrations of H2O and CO_(2),the nature of the catalyst is not irreversibly destroyed and can still return to its initial level of activity.This excellent catalytic activity is attributed to a portion of Rh being uniformly distributed on the CeO_(2) nanorod surface in the form of nanoparticles,forming strong Rh–CeO_(2) interfacial synergy.Another portion of Rh permeated into the CeO_(2) lattice,which results in a significant increase in the number of oxygen vacancies in CeO_(2),thus allowing more surface active oxygen to be adsorbed and converted from the gas phase.Moreover,the catalytic reaction can proceed even in an oxygen-free environment due to the excellent oxygen storage performance of the Rh/CeO_(2) catalyst.
基金supported by the financial aid from National Science and Technology Major Project of China(No.2020YFE0204500)National Natural Science Foundation of China(Nos.22020102003,22025506 and 11975301)Youth Innovation Promotion Association of the Chinese Academy of Sciences(No.2020286)。
文摘The three-way catalyst(TWC),as a promising approach to control automobile exhaust emission,has been widely studied and applied.However,it still suffers from the high light-off temperature and poor stability.Herein,we synthesized a multicomponent catalyst Rh/Cu-CeSn by using Cu metal doping to modify the Ce-based solid solution,which exhibited good TWC catalytic performance:the light-off temperatures for CO,NO,and C_(3)H_(6)conversion are 172℃,266℃,and 193℃,respectively.Moreover,the catalyst still maintained good activity after 12 h of the continuous reaction under high-temperature conditions.The experiments and mechanism studies reveal that due to the redox pair Cu^(+)/Cu^(2+),the Cu incorporation can effectively inhibit the Rh transition to the oxidation state and greatly enhance the catalytic activity and stability.This work provides a viable strategy for precise characteristic modulation of composite oxide supports during the fabrication of noble metal-based catalysts,which significantly reduces environmental pollution from energy applications.
