The novel Ni-Ir/γ-Al2O3 catalyst, denoted as NIA-P, was prepared by high-frequency cold plasma direct reduction method under ambient conditions without thermal treatment, and the conventional sample, denoted as NIA-C...The novel Ni-Ir/γ-Al2O3 catalyst, denoted as NIA-P, was prepared by high-frequency cold plasma direct reduction method under ambient conditions without thermal treatment, and the conventional sample, denoted as NIA-CR, was prepared by impregnation, thermal calcination, and then by H2 reduction method. The effects of reduction methods on the catalysts for ammonia decomposition were studied, and they were characterized by XRD, N2 adsorption, XPS, and H2-TPD. It was found that the plasma-reduced NIA-P sample showed a better catalytic performance, over which ammonia conversion was 68.9%, at T = 450℃, P = 1 atm, and GHSV = 30, 000 h^-1. It was 31.7% higher than that of the conventional NIA-CR sample. XRD results showed that the crystallite size decreased for the sample with plasma reduction, and the dispersion of active components was improved. There were more active components on the surface of the NIA-P sample from the XPS results. This effect resulted in the higher activity for decomposition of ammonia. Meanwhile, the plasma process significantly decreased the time of preparing catalyst.展开更多
In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different no...In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals （Ir, Pt, Pd, Ru, Rh）, supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.展开更多
The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo<sub>2</sub>C/Al<sub>2</sub>O<sub>3</sub> catalyst have been studied by insitu FT-IR spectroscopy.Linearly ad...The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo<sub>2</sub>C/Al<sub>2</sub>O<sub>3</sub> catalyst have been studied by insitu FT-IR spectroscopy.Linearly adsorbed CH<sub>3</sub>CN and CH<sub>3</sub>CH<sub>2</sub>NH<sub>2</sub> were formed after CH<sub>3</sub>CN adsorption on the Mo<sub>2</sub>C/ Al<sub>2</sub>O<sub>3</sub> catalyst.The appearance of a strong band at 1578 cm<sup>-1</sup> indicates that CH<sub>3</sub>CN was reactive with hydrogen on the Mo<sub>2</sub>C/Al<sub>2</sub>O<sub>3</sub> catalyst.展开更多
The surface nature of fresh Mo_2N/Al_2O_3,Mo_2C/Al_2O_3 and M0P/Al_2O_3 catalysts,which were synthesized directly in the IR cell to avoid passivation,were characterized by in situ IR spectroscopy with CO as a probe mo...The surface nature of fresh Mo_2N/Al_2O_3,Mo_2C/Al_2O_3 and M0P/Al_2O_3 catalysts,which were synthesized directly in the IR cell to avoid passivation,were characterized by in situ IR spectroscopy with CO as a probe molecule. CO adsorbed on fresh catalysts showed characteristic IR bands at 2045 cm^(-1) for Mo_2N/Al_2O_3 catalyst,2054 cm^(-1) for Mo_2C/Al_2O_3 catalyst and 2037 cm^(-1) for MoP/Al_2O_3 catalyst,respectively.A strong band at 2200 cm^(-1) for Mo_2N/Al_2O_3 catalyst,which could be ascribed to NCO species formed when CO reacted upon surface active nitrogen atoms,and a weak band at 2196 cm^(-1) for Mo_2C/Al_2O_3 catalyst,which could be attributed to CCO species,were also detected.CO adsorbed on fresh Mo_2N/Al_2O_3 catalyst,Mo_2C/Al_2O_3 catalyst and MoP/Al_2O_3 catalyst,showed strong molecular adsorption,just like noble metals.Our experimental results are bolstered by direct IR evidence demonstrating the similarity in surface electronic property between the fresh Mo_2N/Al_2O_3,Mo_2C/Al_2O_3 and MoP/Al_2O_3 catalysts and noble metals.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 adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibit...The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.展开更多
The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption o...The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.展开更多
研究电流型电化学氨气传感器阳极碳载Ir(Ir/C)催化剂电催化NH3氧化性能.实验表明,在NaC lO4中性电解液中,Ir/C催化剂对NH3氧化的电催化性能与Ir载量有关.其中以Ir载量为10%(by m ass)的Ir/C催化剂的电催化性能最好,稳定性和灵敏度也最高...研究电流型电化学氨气传感器阳极碳载Ir(Ir/C)催化剂电催化NH3氧化性能.实验表明,在NaC lO4中性电解液中,Ir/C催化剂对NH3氧化的电催化性能与Ir载量有关.其中以Ir载量为10%(by m ass)的Ir/C催化剂的电催化性能最好,稳定性和灵敏度也最高.此外,NH3在不同载量的Ir/C催化剂上电催化氧化的电流密度与NH3浓度均呈现出良好的线性关系,此类Ir/C催化剂在电流型电化学氨气传感器中可望有良好的应用前景.展开更多
基金National Natural Science Foundation of China (20590360)New Century Excellent Talent Project of China (NCET-05-0783)
文摘The novel Ni-Ir/γ-Al2O3 catalyst, denoted as NIA-P, was prepared by high-frequency cold plasma direct reduction method under ambient conditions without thermal treatment, and the conventional sample, denoted as NIA-CR, was prepared by impregnation, thermal calcination, and then by H2 reduction method. The effects of reduction methods on the catalysts for ammonia decomposition were studied, and they were characterized by XRD, N2 adsorption, XPS, and H2-TPD. It was found that the plasma-reduced NIA-P sample showed a better catalytic performance, over which ammonia conversion was 68.9%, at T = 450℃, P = 1 atm, and GHSV = 30, 000 h^-1. It was 31.7% higher than that of the conventional NIA-CR sample. XRD results showed that the crystallite size decreased for the sample with plasma reduction, and the dispersion of active components was improved. There were more active components on the surface of the NIA-P sample from the XPS results. This effect resulted in the higher activity for decomposition of ammonia. Meanwhile, the plasma process significantly decreased the time of preparing catalyst.
基金supported by the National Natural Science Foundation of China(No.21106143,No.21277140)100-Talent Project of Dalian Institute of Chemical Physics(DICP)+1 种基金the Independent Innovation Foundation of State Key Laboratory of Catalysis(No.R201113)the Zhejiang Provincial Natural Science Foundation of China(LR12E02001)
文摘In this work, MoOx promoted Ir/SiO2 catalysts were prepared and used for the selective hydrogenolysis of tetrahydrofurfuryl alcohol （THFA） to 1,5-pentanediol in a continuous flow reactor. The effects of different noble metals （Ir, Pt, Pd, Ru, Rh）, supports and Ir contents were screened. Among the investigated catalysts, 4 wt%Ir-MoOx/SiO2 with a Mo/Ir atomic ratio of 0.13 exhibited the best catalytic performance. The synergy between Ix particles and the partially reduced isolated MoOx species attached on them is essential for the excellent catalytic performance of Ix-MoOx/SiO2. The catalyst exhibited a better hydrogenolysis efficiency of THFA with the selectivity of 1,5-pentanediol of 65%-74% at a conversion of THFA of 70%-75% when the initial THFA concentration is ranging from 20 wt% and 40 wt%. And higher system pressure was also in favor of the conversion of THFA. During a stability test, the conversion of THFA and 1,5-pentanediol yield over Ix-MoOz/SiO2 decreased with reaction time, which can be explained by the leaching of Mo species during the reaction.
文摘The adsorption of acetonitrile and its co-adsorption with CO on fresh Mo<sub>2</sub>C/Al<sub>2</sub>O<sub>3</sub> catalyst have been studied by insitu FT-IR spectroscopy.Linearly adsorbed CH<sub>3</sub>CN and CH<sub>3</sub>CH<sub>2</sub>NH<sub>2</sub> were formed after CH<sub>3</sub>CN adsorption on the Mo<sub>2</sub>C/ Al<sub>2</sub>O<sub>3</sub> catalyst.The appearance of a strong band at 1578 cm<sup>-1</sup> indicates that CH<sub>3</sub>CN was reactive with hydrogen on the Mo<sub>2</sub>C/Al<sub>2</sub>O<sub>3</sub> catalyst.
基金supported by the National Nature Science Foundation of China(No.20903054).
文摘The surface nature of fresh Mo_2N/Al_2O_3,Mo_2C/Al_2O_3 and M0P/Al_2O_3 catalysts,which were synthesized directly in the IR cell to avoid passivation,were characterized by in situ IR spectroscopy with CO as a probe molecule. CO adsorbed on fresh catalysts showed characteristic IR bands at 2045 cm^(-1) for Mo_2N/Al_2O_3 catalyst,2054 cm^(-1) for Mo_2C/Al_2O_3 catalyst and 2037 cm^(-1) for MoP/Al_2O_3 catalyst,respectively.A strong band at 2200 cm^(-1) for Mo_2N/Al_2O_3 catalyst,which could be ascribed to NCO species formed when CO reacted upon surface active nitrogen atoms,and a weak band at 2196 cm^(-1) for Mo_2C/Al_2O_3 catalyst,which could be attributed to CCO species,were also detected.CO adsorbed on fresh Mo_2N/Al_2O_3 catalyst,Mo_2C/Al_2O_3 catalyst and MoP/Al_2O_3 catalyst,showed strong molecular adsorption,just like noble metals.Our experimental results are bolstered by direct IR evidence demonstrating the similarity in surface electronic property between the fresh Mo_2N/Al_2O_3,Mo_2C/Al_2O_3 and MoP/Al_2O_3 catalysts and noble metals.
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financially supported by the National Natural Science Foundation of China (No. 21573101)the Liaoning Provincial Natural Science Foundation (No. 2014020107)+1 种基金the Program for Liaoning Excellent Talents in Universities (No. LJQ2014041)sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry (SRF for ROCS, SEM)
文摘The adsorption of acetonitrile, the co-adsorption of acetonitrile with CO, and hydrogenation of acetonitrile on fresh Mo2C/γ-Al2O3 catalyst were studied by in situ IR spectroscopy. It was found out that CH3CN exhibited strong interaction with the fresh Mo2C/γ-Al2O3 catalyst and was adsorbed mainly on Moδ+ sites of fresh Mo2C/γ-Al2O3 catalyst. Moreover, CH3CN could affect the shifting of IR spectra for CO adsorption towards a lower wave number. The IR spectroscopic study on acetonitrile hydrogenation showed that CH3CN could be easily hydrogenated in the presence of H2 on the Mo2C/γ-Al2O3 catalyst. Furthermore, it was observed that CH3 CN could be selectively hydrogenated to imines on fresh Mo2C/γ-Al2O3 catalyst. Additionally, the active sites of fresh Mo2C/γ-Al2O3 catalyst might be covered with coke during the hydrogenation reaction of acetonitrile. The treatment of catalyst with hydrogen at 673 K could not completely remove coke deposits on the surface of the Mo2C/γ-Al2O3 catalyst.
基金financially supported by the National Natural Science Foundation of China(No.20903054)Liaoning Provincial Natural Science Foundation(No.2014020107)+1 种基金Program for Liaoning excellent talents in university(No.LJQ2014041)sponsored by the Scientific Research Foundation for the Returned Overseas Chinese Scholars,State Education Ministry(SRF for ROCS,SEM)
文摘The surface species formed from the adsorption of 1,3-butadiene and 1,3-butadiene hydrogenation over the fresh Mo2C/γ-Al2O3 catalyst was studied by in situ IR spectroscopy. It is found that 1,3-butadiene adsorption on the Mo2C/γ-Al2O3 catalyst mainly forms π-adsorbed butadiene(πs and πd) and σ-bonded surface species. These species are adsorbed mainly on the surface Moδ+(0<δ<2) sites as evidenced by co-adsorption of 1,3-butadiene and CO on the fresh Mo2C/γ-Al2O3 catalyst. The IR spectrometric analysis show that hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst produces mainly butane coupled with a small portion of butene. The selectivity of butene during the hydrogenation of 1,3-butadiene over fresh Mo2C/γ-Al2O3 catalyst might be explained by the adsorption mode of adsorbed 1,3-butadiene. Additionally, the active sites of the fresh Mo2C/γ-Al2O3 catalyst may be covered by coke during the hydrogenation reaction of 1,3-butadiene. The treatment with hydrogen at 673 K cannot remove the coke deposits from the surface of the Mo2C/γ-Al2O3 catalyst.
文摘研究电流型电化学氨气传感器阳极碳载Ir(Ir/C)催化剂电催化NH3氧化性能.实验表明,在NaC lO4中性电解液中,Ir/C催化剂对NH3氧化的电催化性能与Ir载量有关.其中以Ir载量为10%(by m ass)的Ir/C催化剂的电催化性能最好,稳定性和灵敏度也最高.此外,NH3在不同载量的Ir/C催化剂上电催化氧化的电流密度与NH3浓度均呈现出良好的线性关系,此类Ir/C催化剂在电流型电化学氨气传感器中可望有良好的应用前景.
