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
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Shihui Xing,Zhao Liu,Qi Xue,Shiwei Yin,Fumin Li,Weiwei Cai,Shuni Li,Pei Chen,Pujun Jin,Hongchang Yao,Yu Chen
Reducing the overpotential of alcohol oxidation reactions is highly desirable for alkaline direct alcohol fuel cells, but there is still no substantial progress. In this study, unique three-dimensional free-standing Rh nanoroses are synthesized and applied to the isopropanol oxidation reaction. Compared to traditional Pt black electrocatalyst, as-prepared Rh nanoroses exhibit a significant negative shift both in the onset oxidation potential (Δ = 0.223 V) and peak potential (Δ = 0.435 V) as well as 7.5-fold mass activity at 0.3 V for the isopropanol oxidation reaction (IOR) in alkaline electrolyte. The density functional theory calculation indicates the enhanced IOR activity originates form the higher adsorption energy of isopropanol on Rh surface than Pt surface. Since Rh nanoroses have unparalleled activity, this research may bring a new broad of perspective on the isopropanol oxidation reaction.
研究领域:
化学
·
材料科学
·
能源科学
✓ 已验证
产品关联
DOI
高影响因子
Scientific Reports
·
2017
·Vol. 7
·期 1
·1-10
·
IF 4.259
Wang Guojing,Jing Shengchang,Tan Yiwei
Shape control of noble metal (NM) nanocrystals (NCs) is of great importance for improving their electrocatalytic performance. In this report, branched Pd@Rh core@shell NCs that have right square prism-like arms with preferential exposure of Rh {100} facets (denoted as b-Pd@Rh-NCs thereafter) are synthesized and utilized as an electrocatalyst for the hydrazine electrooxidation (HEO) in acidic and alkaline electrolytes. The b-Pd@Rh-NCs are obtained by the heteroepitaxial growth of Rh on the pre-formed branched Pd NCs (denoted as b-Pd-NCs thereafter) core in the presence of poly(vinyl pyrrolidone) (PVP) and bromide ions. A comparative analysis of the voltammetric data for the HEO shows a higher activity on the b-Pd@Rh-NCs exposed with Rh {100} faces than on Rh black, the b-Pd-NCs, and Pd black in acid and alkaline solutions, indicating a structure sensitivity of the reaction. Analysis of the products from the b-Pd@Rh-NCs catalysed HEO reveals a very high hydrazine fuel efficiency, as determined by on-line differential electrochemical mass spectrometry (DEMS).
研究领域:
材料科学
·
电化学
✓ 已验证
DOI
PubMed
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2022
·
IF 24.319
Shihao Li,Yuqing Cheng,Yu Chen,Jing Li,Yiying Sun,Jiafu Shi,Zhongyi Jiang
Electron generation, transfer and utilization in photocatalytic reduction reactions jointly govern the solar-to-chemical conversion efficiency. In natural photosynthesis, the ultrathin thylakoid membrane loads numerous pigments and proteins for light harvesting and electron transfer, which also integrates ferredoxin-NADP + reductase bearing molecule hydrides for electron utilization in NADPH regeneration. Inspired by this, herein, conjugated polymer nanolayer coordinated with (Cp*RhCl 2 ) 2 (CPNL-Rh) is developed through a topological and chemical engineering strategy to synergistically intensify electron generation, transfer and utilization for NADH regeneration. Specifically, the triazine moieties well distributed in CPNL-Rh largely harvest visible light to generate electrons. The electrons are rapidly transferred to Rh cocatalyst through CPNL. Rh cocatalyst finally accepts electrons and protons in solution to form molecule hydrides for implementing NADH regeneration. The turnover frequency of CPNL-Rh for NADH regeneration reaches 44.8 h −1 , among the highest value ever reported and ~346% higher than that of bulk CP with free Rh cocatalyst.
研究领域:
材料科学
·
化学工程
·
光化学
·
催化
✓ 已验证
DOI
高影响因子
ACS Omega
·
2019
·
IF 2.584
Qiuyang Zhang,Caiyun Xu,Hongfeng Yin,Shenghu Zhou
In this work, poly(vinylpyrrolidone)-stabilized 3–5 nm Rh@Co core–shell nanoparticles were synthesized by a sequential reduction method, which was further in situ transformed into Rh-Co2O3 heteroaggregate nanostructures on alumina supports. The studies of XRD, HAADF-STEM images with phase mappings, XPS, TPR, and DRIFT-IR with CO probes confirm that the as-synthesized Rh@Co nanoparticles were core–shell-like structures with Rh cores and Co-rich shells, and Rh-Co2O3 heteroaggregate nanostructures are obtained by calcination of Rh@Co nanoparticles and subsequent selective H2 reduction. The Rh-Co2O3/Al2O3 nanostructures demonstrated enhanced catalytic performance for hydrogenations of various substituted nitroaromatics relative to individual Rh/Al2O3 and illustrated a high catalytic stability during recycling experiments for o-nitrophenol hydrogenation reactions. The catalytic performance enhancement of Rh-Co2O3/Al2O3 nanocatalysts is ascribed to the Rh-Co2O3 interfaces where the Rh-Co2O3 interaction not only prevents the active Rh particles from agglomeration but also promotes the catalytic hydrogenation performance.
研究领域:
材料科学
·
催化化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2022
·Vol. 10
·期 38
·20571-20579
·
IF 14.511
Xue Jiang,Zemeng Dong,Qiong Zhang,Guang-Rui Xu,Jianping Lai,Zhenjiang Li,Lei Wang
The electrochemical oxidation of ethylene glycol (EG), which is favorable for replacing the sluggish oxygen evolution reaction (OER) in thermodynamics, realizes energy-saving hydrogen evolution and also produces high-value chemical products of glycolic acid. Under the guidance of this concept, PtRh nanowires with Rh atom modification (PtRh0.02@Rh NWs), which exhibited excellent properties during the hydrogen evolution reaction (HER) and ethylene glycol evolution reaction (EGOR), were designed and synthesized by controlling the reduction rate of metal precursor through a simple one-step solvothermal reduction. The interface strain effect produced by the metal co-doping effectively adjusted the electronic structure, contributing to introducing the heteroatom active center and inducing lattice strain, thereby achieving excellent electrocatalytic performance. The obtained PtRh0.02@Rh NWs exhibited excellent HER property with an extremely low overpotential of 30.6 and 45.8 mV, and Tafel slope of 39.1 and 39.5 mV dec−1 in alkaline water and seawater electrolytes, respectively, as well as outstanding EGOR properties with peak current density of 1.25 and 1.17 A mg−1, respectively. Additionally, the PtRh0.02@Rh NWs showed superior stability compared to that of commercial platinum black obtained from Johnson Matthey Corporation (JM-Pt black). When using PtRh0.02@Rh NWs as biofunctional materials for the HER in the cathode and the EGOR in the anode, a cell voltage of only 0.66 V for PtRh0.02@Rh NWs (HER)‖PtRh0.02@Rh NWs (EGOR) achieved a current density of 10 mA cm−2, which was much smaller than that of PtRh0.02@Rh NWs (HER)‖PtRh0.02@Rh NWs (OER) at 1.57 V. The results of electrochemical in situ Fourier transform infrared (FTIR) spectroscopy showed that the synthesized PtRh0.02@Rh NWs promoted the production of high-value glycolic acid when EG was dehydrogenated to form C2 intermediates. The Rh atoms modified on the surface of the Pt nanowires provided an effective strain effect to optimize the active sites, which creates a universal strategy for the design of highly efficient and durable bifunctional catalysts.
研究领域:
电化学
·
材料科学
·
催化反应
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Ziqiang Wang,Guanghui Yang,Pengjun Tian,Xinmiao Li,Kai Deng,Hongjie Yu,You Xu,Hongjing Wang,Liang Wang
The use of thermodynamically more favorable sulfion oxidation reaction (SOR) to replace sluggish oxygen evolution reaction is an effective method for energy-saving production of hydrogen. Herein, we propose the synthesis of organic–inorganic hybrid through the modification of 1-hydroxyethylidene-1,1-diphosphonic acid on Rh metallene (HEDP-Rh metallene) as a bifunctional electrocatalyst for hydrogen evolution reaction (HER) and SOR. The modification of hydrophilic HEDP can effectively promote the water adsorption, thereby accelerating the mass/electron transfer at the interface. The HEDP-Rh metallene requires low overpotentials of 30 mV at 10 mA cm −2 for HER and 0.538 V at 100 mA cm −2 for SOR. In HER-SOR coupled reaction, HEDP-Rh metallene drives the current density of 100 mA cm −2 at 1.08 V for concurrent production of hydrogen and sulfur, highlighting energy-efficient hydrogen production and sulfur recycle.
研究领域:
材料科学
·
能源化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2020
·
IF 16.683
Qi Xue,Hao Huang,Jing-Yi Zhu,Yue Zhao,Fu-Min Li,Pei Chen,Yu Chen
Optimizing morphology, structure, and composition of noble metal bimetallic nanomaterials not only enhances their electroactivity and stability but also expands their scope of application. In this work, ultrafine bimetallic Au@Rh core-shell nanowires (Au@Rh ultra-NWs) are synthesized by simple wet chemical strategy using ultrafine Au nanowires (Au ultra-NWs) with 5.50 nm diameter as substrate and explore their potential application for hydrazine electro-oxidation reaction (HeOR) in an alkaline solution. Experimental and calculational results demonstrate that bimetallic Au@Rh ultra-NWs with optimal component reveal 13.6-fold Rh-mass activity enhancement for HeOR at 0.4 V potential relative to commercial Rh nanocrystals (Rh c-NCs), which can be ascribed to the ultrathin Rh shell thickness and the electronic effect caused by the interaction between Au core and Rh shell. Under light irradiation conditions, bimetallic Au@Rh ultra-NWs further show plasmon-promoted HeOR activity, which originates from photoelectric and photothermal effects caused by localized surface plasmon resonance of Au ultra-NWs core.
研究领域:
化学
·
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2019
·
IF 14.229
Jing-Yi Zhu,Shiqian Chen,Qi Xue,Fu-Min Li,Hong-Chang Yao,Lai Xu,Yu Chen
Hierarchical porous precious metal-based nanosheets with ultrathin structures and highly exposed active surfaces are desirable in energy conversion technology, while robust synthetic strategies remain challenging. Here, we report a facile 1-hydroxyethylidene-1,1-diphosphonic acid (HEDP)-mediated approach to synthesize hierarchical porous Rh nanosheets (HP-Rh NSs), following the formation mechanism of emulsion-induced soft template. When HP-Rh NSs are applied to the methanol oxidation reaction (MOR), abundant edge/grain-boundary atoms and the ultrathin porous structure endow HP-Rh NSs with a mass activity of 333 A g −1 at 0.63 V, which are 5.8-fold enhancements compared with traditional commercial Pt black (57.4 A g −1 ). Meanwhile, the peak potential of MOR on HP-Rh NSs is 0.2 V lower than that on commercial Pt black. With the aid of theoretical calculations, larger methanol adsorption energy and the lower energy barrier reaction path are responsible for superior MOR activity on Rh HP-Rh NSs than commercial Pt black.
研究领域:
材料科学
·
能源技术
·
催化化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Zenan Hu,Junjie Zhou,Yongjian Ai,Lei Liu,Li Qi,Ruihang Jiang,Hongjie Bao,Jingting Wang,Jianshe Hu,Hong-bin Sun,Qionglin Liang
A magnetically separable 2D Rh/Fe 3 O 4 /g-C 3 N 4 -N catalyst has been synthesized for the catalytic transfer hydrogenation of nitroarenes to afford corresponding anilines. The highly dispersed Rh nanoparticles are the dominant active species. The reaction is second order for rhodium according to the kinetic study, and this means the activity of different Rh-containing catalyst can be precisely predicted and the active site contains two adjoining rhodium atoms. The strong interaction between Rh and Fe 3 O 4 contributes to the catalytic performance, therefore the obtained Rh/Fe 3 O 4 /g-C 3 N 4 -N catalyst exhibits excellent catalytic activity and chemoselectivity for the reduction of various nitroaromatics, and the turnover frequencies (TOF) can reach as high as 12,666 h −1 for 4-nitrophenol. Moreover, this catalytic system is environmentally friendly because of its green solvent water and harmless byproducts (H 2 O and N 2 ), and the catalyst shows outstanding stability and recyclability with at least 12 cycles.
研究领域:
化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
·
2025
·
IF 6.3
Xia Wei,Bing Fang,Tianyao Wang,Hongbin Dai,Song Li
Understanding the metal-support interaction between Rh-B and CeO 2 is essential for enhancing the efficiency of hydrogen generation from hydrous hydrazine. In this study, a series of Rh-B/CeO 2 catalysts were synthesized via a facile wet-chemical reduction method. The Rh-B/(CeO 2 ) 0.7 catalyst exhibits a remarkable 12-fold increase in turnover frequency (TOF) compared to pristine Rh-B catalyst. The strong electronic coupling between Rh-B and CeO 2 was identified as the primary factor driving this significant performance enhancement. This interaction facilitates the formation of oxygen vacancies, promoting hydrazine adsorption and subsequent cleavage of the N-H bond in N 2 H 4 * to form N 2 H 3 *. Our findings emphasize the pivotal role of support engineering in catalyst design for optimizing catalytic performance.
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
Nature Catalysis
·
2024
·Vol. 7
·期 6
·666-677
·
IF 42.8
Dou Xiaomeng,Yan Tao,Qian Lixiang,Hou Huaming,Lopez-Haro Miguel,Marini Carlo,Agostini Giovanni,Meira Debora M.,Zhang Xiangjie,Zhang Liang,Cao Zhi,Liu Lichen
Achieving the regioselective hydroformylation of linear α-olefins to linear aldehydes using solid catalysts with regioselectivities comparable to the corresponding homogeneous process is a great challenge in the chemical industry. Despite the tremendous efforts devoted to this research topic, most of the reported heterogeneous metal catalysts still give considerably lower regioselectivities than well-established homogeneous metal catalysts. Here we show the design of efficient Rh-zeolite catalysts, in which subnanometre Rh clusters are selectively confined in the sinusoidal ten-membered-ring channels of MFI zeolite, for the hydroformylation of long-chain linear α-olefins (C 6 –C 12 ) into linear aldehydes with very high linear-to-branched aldehyde ratios (up to 400). The exceptional catalytic performances result from the involvement of the MFI zeolite framework as a rigid solid ligand that accommodates subnanometre Rh clusters in the sinusoidal channels of the MFI zeolite.
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
危险品化学品经营许可证（带存储）