DALTON TRANSACTIONS
·
2023
·Vol. 52
·期 39
·13955-13961
·
IF 4
Xiaorui Yan,Lele Chen,Haisheng Wei,Tiantian Liu,Kairui Li,Jing Li
The stability of Rh-based heterogeneous catalysts is a key issue in the hydroformylation of olefins. Confinement of active Rh species has been considered an effective strategy to achieve stable catalysts. In this work, a phosphine ligand was successfully confined in ZIF-8 material and coordinated with Rh metal by a reduction procedure to develop an efficient and stable Rh-based catalyst for hydroformylation of 1-octene. The results indicate that the catalyst reduced at 300 °C under H2 atmosphere exhibits better stability than that with NaBH4 as reductant and undoped P catalyst. Various characterization studies demonstrate that the superior performance is due to the strong interaction between Rh metal and P, which inhibits the leaching of active Rh species. This work reveals an effective strategy for the synthesis of highly stable catalysts for use in the hydroformylation reaction.
研究领域:
催化
·
化学工程
·
材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Guangjun Ji,Cunyao Li,Pan Gao,Miao Jiang,Lei Ma,Guoqing Wang,Guangjin Hou,Li Yan,Yunjie Ding
Tuning the microenvironment surrounding single atom metals is an effective but challenging way to regulate the performance of single atom catalysts (SACs). Herein, we prepared a series of P, N-abundant porous organic polymers (P&N-POPs) with diverse framework flexibility and coordination ability to serve as SACs’ carriers. The microenvironment (coordination site, coordination number) surrounding Rh and the equilibrium of ea / ee -HRh(CO) 2 P 2 active species were effectively regulated in Rh/P&N-POPs catalysts. Our study shows that the specific active ee -HRh(CO) 2 (P) 2 species confined in the flexible polymeric skeleton endowed the Rh/ m PPh 3 &PPD-POP with superior activity (TOF = 2000 h −1 ), selectivity of aldehydes (93.5 %), ratio of linear aldehyde to branched aldehyde (l/b ratio = 15.9), favorable stability (10 recycling runs without activity loss) and extensive substrate applicability (19 kinds of olefins) in hydroformylation reactions. Multiple characterization techniques (EXAFS, STEM, in-situ FTIR etc.) were employed to get insights into this effective strategy to regulate the performance of single atom catalysts (SACs).
研究领域:
催化化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
MICROPOROUS AND MESOPOROUS MATERIALS
·
2010
·
IF 2.652
Wan-Zhong Lang,Xun-Wen Liu,Ya-Jun Guo,Bo Su,Lian-Feng Chu,Cui-Xiang Guo
We have demonstrated the synthesis of a novel MCM-41-supported bi-functional catalyst containing organoamine and Rh–P complex. We further characterized the catalysts by state-of-the-art analytical techniques including FTIR, UV–vis, 31 P CP MAS NMR, TGA, XRD, BET, TEM, ICP-AES and elemental analysis. The as-synthesized catalyst was applied to the one-pot synthesis of 2-ethylhexenal using propene as raw materials. FTIR, UV–vis, 31 P CP MAS NMR, and TGA results indicate that the active sites, organoamine and Rh–P complex, are successfully immobilized on the surface of catalyst support. The N and Rh content can be adjusted by adding different amounts of organoamine and Rh–P complex during the process of catalyst preparation. The mesoporous structure of the zeolite support remains intact after immobilization. However, the specific surface area and BJH pore size of the mesoporous zeolite support decrease after being grafted with organoamine and Rh–P complex. The bi-functional catalyst with primary amine has the best catalytic performances for the one-pot synthesis of 2-ethylhexenal since it has better synergistic effect with silanol groups, followed by diamine and then tertiary amine. The Rh content of the catalyst determines the hydroformylation reaction rate of propene, while the self-condensation of n -butanal is determined by the balance between organoamine and silanol groups. The results indicate the hydroformylation reaction is the control step of this tandem reaction when the content of Rh in the catalyst is below 0.19%. In contrast, this tandem reaction is controlled by the self-condensation of n -butanal with further increasing Rh content. We found that the catalyst containing 1.73% of N (primary amine) and 0.19% of Rh is a suitable choice. And we obtained the best yield of 2-ethylhexenal above 77% in the one-pot synthesis from propene.
研究领域:
催化化学
·
材料化学
·
有机合成
·
多相催化
·
功能材料
·
工业化学
✓ 已验证
DOI
高影响因子
Journal of Materials Chemistry A
·
2021
·Vol. 9
·期 14
·9157-9164
·
IF 12.732
Zhiwei Chen,Yang Li,Lin Wang,Yuyu Bu,Jin-Ping Ao
In this paper, a MoS2/Rh–P bi-compound heterogeneous cocatalyst is developed to improve the photoelectrochemical (PEC) water splitting performance of a p-Si photocathode. Compared with the single cocatalysts (MoS2 and Rh–P), the bi-compound heterogeneous cocatalyst MoS2/Rh–P on the p-Si photocathode surface exhibits a much better hydrogen evolution reaction (HER) activity at the electrode/electrolyte interface, which is attributed to the synergistic electronic effect between MoS2 and Rh–P materials. Meanwhile, the TiO2 layer could serve as a linker between p-Si and the surface cocatalyst to optimize the interface energy, further promoting the photocarrier transfer process within the system. Thus, the as-prepared p-Si–TiO2–MoS2/Rh–P photocathode exhibits excellent PEC performance with a high photocurrent density of −24.1 mA cm−2 at 0 V (vs. RHE) and a positive onset potential of 0.43 V (vs. RHE). And the bi-compound heterogeneous cocatalyst provides a feasible strategy for boosting the PEC hydrogen evolution.
研究领域:
材料科学
·
能源转换与存储
✓ 已验证
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）