ACS Applied Energy Materials
·
2021
·
IF 6.024
Lin-Chang Liu,Hong-Lin Zhu,Yue-Qing Zheng
Ammonia borane (NH3BH3, referred to as AB) hydrolytic dehydrogenation is regarded as a feasible strategy for hydrogen production owing to its high hydrogen content, pollution-free nature, and high stability. Metal nitrogen-doped carbon materials (M-N-C) are considered as an ideal candidate support of catalysts with AB hydrolytic dehydrogenation due to the advantages of low cost, large specific surface area, rich defective site, and good chemical stability. In this work, tubular Ni@Ni-N-C was successfully synthesized by high-temperature pyrolysis, and then, Rh nanoparticles were decorated on the support Ni@Ni-N-C by impregnation and reduction to prepare a series of Rh/Ni@Ni-N-C. The best catalytic performance of catalysts is obtained using Ni@Ni-N-C with an Rh loading of 0.74 wt %, showing a turnover frequency as high as 782.18 min–1 and an apparent activation energy (Ea) as low as 25.86 kJ mol–1, which could be attributed to the strong interaction between Rh and the defective site of the support.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
Molecular Catalysis
·
2021
·
IF 5.062
Xiao Li,Liusha Li,Tingting Qin,Gong Gun,Tiejun Lin,Liangshu Zhong
Tandem hydroaminomethylation is an efficient and green route for one-pot synthesis of amines directly from olefins. Herein, heterogeneous hydroxyapatite (HAP) supported single-atom Rh catalyst was prepared and used for tandem hydroaminomethylation of olefins. Characterization techniques confirmed the atomic dispersion of Rh species on HAP. Up to 99% conversion of 1-hexene with high selectivity to the desired amines (93.2%) was obtained over 0.5Rh 1 /HAP catalyst. Mechanism study demonstrated that the first hydroformylation step during the tandem catalytic process was rate-determining. Compared with the Rh nanoparticles on other oxide supports (Mg 3 Al, MgO and Al 2 O 3 ), the atomically dispersed Rh sites on HAP ensured the high hydroformylation activity, thereby guaranteed the outstanding catalytic performance for the total tandem process. Furthermore, various corresponding amines can be obtained with satisfactory yields over 0.5Rh 1 /HAP catalyst from a wide scope of olefins or amines substrates.
研究领域:
催化化学
·
材料科学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2017
·
IF 4.339
Yuqing Wang,Li Yan,Cunyao Li,Miao Jiang,Wenlong Wang,Yunjie Ding
Porous organic copolymer (denoted as CPOL-BP&P) was afforded through the copolymerization of vinyl biphephos and tris (4-vinylphenyl)phosphine monomers under solvothermal conditions, and followed with impregnation method provided a highly efficient Rh/CPOL-BP&P catalyst with high activity (TOF = 11,200 h −1 ) and regioselectivity (the ratio of linear to branched aldehydes, l:b = 62.2) for heterogeneous hydroformylation of 1-butene. High regioselectivity was also obtained in the hydroformylation of butene mixture (2-butene: l:b = 55.8, isomeric mixture of butenes: l:b = 56.0). The Rh/CPOL-BP&P catalysts were thoroughly characterized by means of nitrogen sorption isotherms, in situ FT-IR, XPS, solid-state 31 P MAS NMR, HAADF-STEM, SEM and TEM. The formation of unique coordination bonds with Rh species in the polymer skeleton was determined. Heterogeneous hydroformylation of butenes was effectively realized due to a synergetic effect between PPh 3 moiety and biphephos moiety.
研究领域:
材料化学
·
催化化学
✓ 已验证
DOI
高影响因子
Science Bulletin
·
2021
·
IF 11.78
Yang Li,Xian Wang,Bingbao Mei,Ying Wang,Zhaoyan Luo,Ergui Luo,Xiaolong Yang,Zhaoping Shi,Liang Liang,Zhao Jin,Zhijian Wu,Zheng Jiang,Changpeng Liu,Wei Xing,Junjie Ge
Proton exchange membrane fuel cells (PEMFCs) suffer extreme CO poisoning even at PPM level (<10 ppm), owning to the preferential CO adsorption and the consequential blockage of the catalyst surface . Herein, however, we report that CO itself can become an easily convertible fuel in PEMFC using atomically dispersed Rh catalysts (Rh-N-C). With CO to CO 2 conversion initiates at 0 V, pure CO powered fuel cell attains unprecedented power density at 236 mW cm −2 , with maximum CO turnover frequency (64.65 s −1 , 363 K) far exceeding any chemical or electrochemical catalysts reported. Moreover, this feature enables efficient CO selective removal from H 2 gas stream through the PEMFC technique, with CO concentration reduced by one order of magnitude through running only one single cell, while simultaneously harvesting electricity. We attribute such catalytic behavior to the weak CO adsorption and the co-activation of H 2 O due to the interplay between two adjacent Rh sites.
研究领域:
能源科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Zhou Ren,Yang Liu,Yuan Lyu,Xiangen Song,Changyong Zheng,Siquan Feng,Zheng Jiang,Yunjie Ding
A novel Rh based porous composed N polymer with hierarchical pore, high surface area and high thermal stability (Rh-POL-2BPY) was successfully obtained by impregnation of Rh 2 (CO) 4 Cl 2 solution of dichloromethane. And based on Rh species as the most active carbonylation site, Rh-POL-2BPY was selected as a catalyst applied in heterogeneous methanol carbonylation system and behaved excellent carbonylation activity (TOF ≈ 1400 h −1 ) under 195 °C, 2.5 MPa, higher than the corresponding homogeneous system without acetic acid. In addition, contrast to the most reported unstable heterogeneous methanol carbonylation systems, Rh-POL-2BPY could maintain incredibly outstanding stability for near 400 h owing to the firm coordination bond between Rh and N and high exposed N content in the polymer. Here, POL-2BPY apart from its heat-resisting property acts as massive rivets to immobilize the Rh species in its framework solidly during carbonylation process. XPS, XANES, HAADF-STEM and EXAFS results verify the N species of bipyridine, the single atom dispersion of Rh and Rh N coordination bond. And above all, the novel five-coordinated Rh center is proposed as the real active site of methanol carbonylation by EXAFS spectra.
研究领域:
化学工程
·
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL
·
2015
·
IF 3.615
Sheng-Jie Chen,Yong-Qi Li,Peng Wang,Yong Lu,Xiao-Li Zhao,Ye Liu
Two kinds of novel zwitterionic phosphines of L1 and L2 have been synthesized in which the sulfonate groups (–SO 3 – ) are incorporated to render them amphiphilic. Both of them are strong π-acceptor ligands in which the positive-charged imidazoliums with intensive electron-withdrawing effect are vicinal to the coordinating phosphorous atoms. The amino-group of piperidyl is additionally incorporated in L2 to make it behave as a hybrid ligand with potential hemilability. The comparison of the ligands of L1 and L2 in Rh-catalyzed hydroformylation of styrene (and its derivatives) and the effect of water on their behaviors were discussed. Without the involvement of water, the catalytic system of Rh(acac)(CO) 2 - L2 exhibited lower activity than that of Rh(acac)(CO) 2 - L1 under the same conditions. However, the dramatic promotion effect of water as a suspension was observed especially for Rh(acac)(CO) 2 - L2 system with TOF spurred up from 195 to 470 h −1 . The corresponding in situ high pressure FT-IR spectral information showed that the presence of water in Rh(acac)(CO) 2 - L2 system greatly facilitated the formation and stability of the active Rh–H species ( ν Rh-H , 2047 cm −1 ), which was in charge of the efficient hydroformylation of styrene and its derivatives.
研究领域:
有机化学
·
催化化学
✓ 已验证
DOI
高影响因子
GREEN CHEMISTRY
·
2016
·Vol. 18
·期 10
·2995-3005
·
IF 8.506
Cunyao Li,Li Yan,Lanlu Lu,Kai Xiong,Wenlong Wang,Miao Jiang,Jia Liu,Xiangen Song,Zhuangping Zhan,Zheng Jiang,Yunjie Ding
A vinyl functionalized biphephos ligand with high steric hindrance was copolymerized with tris(4-vinphenyl)phosphane and other ligands to afford efficient porous organic copolymers (POPs) through the solvothermal synthesis technique. By employing the copolymer self-supported heterogeneous Rh/CPOL-bp&P catalysts, the hydroformylation of propene to linear-butaldehyde can be performed efficiently in a continuous fixed-bed reactor with high regioselectivity (l/b > 24), activity (TOF > 1200 h−1) and stability (over 1000 h) under mild conditions (70 °C, 0.5 MPa), which represents a substantial improvement in the efficiency of this important industrial process. EXAFS and HAADF-STEM showed that the Rh was a single atom dispersion, which explained well the high efficiency of the Rh/CPOL-bp&P catalysts. Compared with liquid–liquid biphasic (LLB) and ionic liquid (IL) systems, this highly efficient solvent free system has the advantages of simple operability, and almost no waste emission, which meets the demands of green industrial processing.
研究领域:
化学工程
·
催化材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2025
·
IF 13.2
Guangjun Ji,Cunyao Li,Benhan Fan,Guoqing Wang,Zhao Sun,Miao Jiang,Lei Ma,Li Yan,Yunjie Ding
Rational designing the structure of catalysts is an effective but challenging way to optimize catalytic performance for target reaction, which is especially significative in the field of single site catalysts. In this work, a kind of single Rh catalysts for heterogeneous hydroformylation of olefins with CO 2 as substituted carbonyl sources was designed. By simply doping N sites surround Rh P active sites, Rh 1 /POPs-P&N were endowed with better catalytic performance even than homogeneous Rh P complex catalysts. Our study showed that the fine fabricated skeleton structure of Rh 1 /POPs-P&N could endow the N sites with function promotion effect on the adjacent Rh P active sites to different degrees. Consequently, the Rh 1 / m -POP-PPh 3 &PMPD, which formed more HRh(CO) 2 (P) 2 species during the reaction, exhibited the highest yield of aldehydes (conversion of 89 %, selectivity toward aldehydes of 87.1 %, l/b ratio of 13.1), good stability (5 recycling runs without activity loss) and extensive substrate applicability (12 kinds of olefins) in heterogeneous hydroformylation of olefins with CO 2 , surpassing all homogeneous and heterogeneous catalysts that only contain Rh P sites (Table 5). Multiple characterization techniques (EXAFS, STEM, in-situ FTIR etc. ) were employed to get insights into this effective strategy to rationally design efficient single site catalysts.
研究领域:
催化
·
材料科学
·
化学反应工程
·
无机化学
·
绿色化学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）