JOURNAL OF CATALYSIS
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2023
·
IF 7.3
Yuanjie Xu,Zemin An,Xin Yu,Jikang Yao,Qian Lv,Hua Yang,Zhengang Lv,Huichuang Guo,Qike Jiang,Wei Liu,Lizhi Wu,Li Tan,Yihu Dai,Yu Tang
Strong metal-support interaction (SMSI) is a crucial factor that determines the structure and performance of a supported metal catalyst. Herein, the SMSI effect of Rh nanoparticle catalyst supported on h-BN is investigated in the dry reforming of methane (DRM) reactions with different CO 2 /CH 4 ratios. The catalyst characterization results demonstrate that the SMSI effect allows the Rh nanoparticles to be encapsulated by BO x overlayers under DRM reaction conditions (CO 2 /CH 4 = 1/1), which prevents the interaction between the reactants and metal centers for causing rapid deactivation. By increasing the partial pressure of CO 2 (CO 2 /CH 4 = 3/1), Rh/BN exhibits significantly enhanced activity and long-term stability in the DRM reaction. CO 2 or H 2 O in the reactive atmosphere can effectively etch the BO x overlayers for steadily exposing the active Rh-BN interface sites, as evidenced by the characterization. This observation extends the understanding of the SMSI effect at the interfaces between metal and non-oxide support.
研究领域:
催化化学
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材料科学
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DOI
高影响因子
APPLIED ORGANOMETALLIC CHEMISTRY
·
2024
·Vol. 38
·期 11
·e7685
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IF 3.7
Ze-Nan Hu,Fangya Guo,Xiuxiu Zhang,Jie Yu,Yaru Yin,Biying Zhang,Hua-Jun Chen,Meijia Chang,Yiming Wang,Yalei Miao,Lan Zhang,Wenjie Tian,Hong-bin Sun
Hydrazine hydrate as a hydrogen source has a good effect on nitro reduction, but overuse has environmental toxicity and is prone to over-hydrogenation, resulting in low selectivity. Herein, we report a magnetically separable Rh/Fe 3 O 4 (1.26 wt%) catalyst containing an optimal Rh content that can completely convert 3-nitrostyrene to 3-vinylaniline (> 99% selectivity) using a stoichiometric molar ratio of hydrazine hydrate (-NO 2 :N 2 H 4 ·H 2 O = 1:1.5). This is due to the synergy between Rh and Fe 3 O 4 and the natural selectivity of N 2 H 4 ·H 2 O for nitro. The synergy can reduce the activation energy of the reaction (36.6 kJ/mol), increasing the reduction rate of nitro group and avoiding the combination of active hydrogen species (H*) to H 2 as well as the hydrogenation of N 2 H 4 to NH 3 . Moreover, the active H* produced by N 2 H 4 ·H 2 O is different from that produced by H 2 , and excess dose of N 2 H 4 will inevitably yield H 2 thus decline the selectivity.
研究领域:
催化
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化学工程
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材料科学
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高影响因子
ENVIRONMENTAL SCIENCE & TECHNOLOGY
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2024
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IF 10.8
Hao Liu,Shan Yang,Jinxing Mi,Chuanzhi Sun,Jianjun Chen,Junhua Li
N2O and CO coexist in various industrial and mobile sources. The synergistic reaction of N2O and CO to generate N2 and CO2 has garnered significant research interest, but it remains extremely challenging. Herein, we constructed an atomically dispersed Rh-supported CeO2 catalyst with asymmetric Rh–O–Ce sites through gradient Rh 4d–O 2p–Ce 4f orbital coupling. This design effectively regulates the 4f electron states of Ce and promotes the electron filling of the O 3π* antibonding orbital to facilitate N–O bond cleavage. Near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) reveals that CO reacts with the surface-adsorbed O* generated by N2O decomposition through self-tandem catalysis, accelerating the rate-limiting step in N2O decomposition and activating the synergistic reaction of N2O and CO at temperatures as low as 115 °C. This work can guide the development of high-performance catalysts using the strategy of high-order orbital hybridization combined with the tandem concept to achieve versatile catalytic applications.
研究领域:
催化化学
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环境科学
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材料科学
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DOI
PubMed
高影响因子
Molecular Catalysis
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2022
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IF 5.089
Cheng Yang,Maoshuai Li,Weikang Dai,Jie Wei,Qi Yang,Yi Feng,Wanxin Yang,Jie Ding,Ying Zheng,Mei-Yan Wang,Xinbin Ma
The homogeneous catalytic hydroformylation of formaldehyde to glycolaldehyde is a key intermediate step for one-step synthesis of ethylene glycol from syngas. The effect of solvent nature on the catalytic response and mechanistic pathway has been rarely studied. A group of parameters (e.g., ε r , μ, α, β) describing the solvent electronic features were achieved for a descriptor database and correlated with the hydroformylation activity. The net electron donating ability has been found to govern the selectivity to glycolaldehyde. The DFT calculation demonstrates the stronger electron-donating solvents serve to lower the energy required for the dissociation of Rh-H to form the anionic rhodium species, which induces the anion mechanism that preferentially facilitates the glycolaldehyde generation. The polar aprotic solvents can be protonated in the dissociation of Rh-H to the anionic species and participate in the HCHO activation through the proton transfer from solvent molecules to HCHO, resulting in the formation of hydroxymethyl species.
研究领域:
催化
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化学工程
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物理化学
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材料科学
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DOI
高影响因子
JOURNAL OF CATALYSIS
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2025
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IF 6.5
Haolin Luo,Junie Jhon M. Vequizo,Zhen Ye,Feng Han,Jiasheng Chi,Jiawei Yan,Akira Yamakata,Wenfeng Shangguan,Zhi Jiang
Facet-engineered semiconductor single crystals hold considerable promise for applications ranging from solar fuels to photovoltaics. However, solid-state syntheses, though operationally simpler, typically fail at facet control due to limited atomic mobility, whereas solution/flux-based methods rely heavily on additives. Herein, we report a straightforward, self-directing solid-state ion doping strategy for synthesizing well-defined cuboidal rhodium-doped SrTiO 3 (SrTiO 3 :Rh) single-crystalline particles with predominant (1 0 0)/(0 1 0) facet exposure. This strategy is based on the identification of a previously unrecognized dual role of ionic Rh precursors as intrinsic structure-directing agents and visible-light sensitizers, facilitating concurrent crystal growth, facet stabilization and controlled doping incorporation during a single calcination step. Compared to Rh 2 O 3 -derived SrTiO 3 :Rh, a milestone photocatalyst historically suffered from poor facet control, these cuboidal crystals with anisotropic electronic surface structures exhibited enhanced crystallinity, superior charge separation efficiency and accelerated surface reaction kinetics, resulting in an order-of-magnitude improvement in visible-light-driven hydrogen evolution. Notably, when integrated into a liquid-phase Z-scheme system with BiVO 4 and Fe 3+ /Fe 2+ redox mediators, the SrTiO 3 :Rh single crystals exhibited a remarkable apparent quantum yield of 3.2 % at 420 nm for overall water splitting. This facile, self-directing synthetic approach addresses key challenges in traditional solid-state routes, providing valuable guidance for rational facet and doping engineering in diverse functional semiconductors for energy conversion.
研究领域:
材料科学
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光催化
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能量转换
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半导体工程
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太阳能燃料
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DOI
高影响因子
Nature Communications
·
2023
·Vol. 14
·期 1
·1-10
·
IF 16.6
Wang Yi,Yang Rong,Ding Yajun,Zhang Bo,Li Hao,Bai Bing,Li Mingrun,Cui Yi,Xiao Jianping,Wu Zhong-Shuai
Exploring durable electrocatalysts with high activity for oxygen evolution reaction (OER) in acidic media is of paramount importance for H 2 production via polymer electrolyte membrane electrolyzers, yet it remains urgently challenging. Herein, we report a synergistic strategy of Rh doping and surface oxygen vacancies to precisely regulate unconventional OER reaction path via the Ru–O–Rh active sites of Rh-RuO 2 , simultaneously boosting intrinsic activity and stability. The stabilized low-valent catalyst exhibits a remarkable performance, with an overpotential of 161 mV at 10 mA cm −2 and activity retention of 99.2% exceeding 700 h at 50 mA cm −2 . Quasi in situ/operando characterizations demonstrate the recurrence of reversible oxygen species under working potentials for enhanced activity and durability. It is theoretically revealed that Rh-RuO 2 passes through a more optimal reaction path of lattice oxygen mediated mechanism-oxygen vacancy site mechanism induced by the synergistic interaction of defects and Ru–O–Rh active sites with the rate-determining step of *O formation, breaking the barrier limitation (*OOH) of the traditional adsorption evolution mechanism.
研究领域:
材料科学
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电化学
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催化
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能源材料
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DOI
PubMed
高影响因子
Journal of Materials Chemistry A
·
2018
·Vol. 6
·期 24
·11337-11345
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IF 9.931
Wei-Ming Liao,Jian-Hua Zhang,Zheng Wang,Shao-Yun Yin,Mei Pan,Hai-Ping Wang,Cheng-Yong Su
Electron-deficient Ru/Rh half-sandwich units are optoelectronical, stereochemical, and redox and catalytically active in nature. Four different species of these units were designed and successfully incorporated into UiO-67 frameworks by post-synthetic exchange (PSE) method and employed for photocatalytic H2 evolution and CO2 reduction. Among them, the PSE-MOF catalysts containing [M–OH2] (M = Rh or Ru) groups show higher photocatalytic activity than those with [M–Cl], providing a new example of the exploitation of H2O molecules as small ancillary ligands for the construction of Ru/Rh half-sandwich units and subsequent incorporation into MOFs as photocatalytic centers. The application of TEOA (triethanolamine) and DMA (N,N-dimethylaniline) as sacrificial agents leads to different catalytic mechanisms and durations. A long-term hydrogen evolution lasting for 174 h without significant decrease in efficiency was achieved in the RhOH2@UiO-DMA system, showing the advantage of PSE-MOFs as highly stable photocatalytic platforms with superior self-protective properties.
研究领域:
材料科学
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催化化学
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DOI
高影响因子
Journal of Environmental Chemical Engineering
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2024
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IF 7.4
Yifei Chen,Yongru You,Chen Xin,Xiuqin Dong,Hao Gong
The diverse pore structures and excellent tunable proprieties of IRMOFs materials made the possibility to explore the effect of the mode of ligand-immobilization on its catalytic performance for 1-butene hydroformylation. In this work, we report a successful case of theory-guided rational design of a highly active ligand-immobilized Rh/IRMOF catalyst based on previous work. Density functional theory calculations of elementary reaction barriers for 1-butene hydroformylation over 1Rh/IRMOFs-PPh 3 models (IRMOF-1, -8, -10, -14, and -16) were performed. The calculation results and topographic steric maps analysis predicted that 1Rh/IRMOF-10-PPh 3 have superior catalytic performance. This can be attributed to the “shape-selective” effect of phosphine ligands grafted in the backbone on the reactive transition state. In addition, the anchoring positions of the phenyl phosphine ligand grafting on the skeleton of 1Rh/IRMOF-10-PPh 3 was identified in details. The 1Rh/IRMOF-10-PPh 3 [3‐3] was predicted to have the highest n/i ratio. In order to verify the theoretical prediction, 1Rh/IRMOF-10–32PPh 3 catalyst was prepared by post-synthesis strategy and the n/i ratio was experimentally confirmed to be 3.49, which outperform the previous 1Rh/MOF-5-PPh 3 catalyst. This work suggests that the 1Rh/IRMOF-10-PPh 3 catalyst can be a promising catalyst for hydroformylation reactions.
研究领域:
催化
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材料科学
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化学工程
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计算化学
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DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2022
·Vol. 32
·期 31
·2201081
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IF 19.924
Qiqi Mao,Kai Deng,Hongjie Yu,You Xu,Ziqiang Wang,Xiaonian Li,Liang Wang,Hongjing Wang
Designing efficient and durable electrocatalysts for seawater electrolysis shows a great research prospect, but it remains a significant challenge. Herein, we report the partially hydroxylated Rh metallene (Rh/RhOOH metallene) with porous, ultrathin, defect-rich and hetero-phase structure for ethylene glycol (EG)-assisted seawater electrolysis. In parallel, the unique redox effect of RhOOH species and EG as well as the electroreduction effect riggers the in situ reconstruction for the catalyst during electrocatalysis, which further produces active Rh species to optimize the catalytic activity center and surface catalytic reaction. Benefiting from the unique metallene structure and the Rh/RhOOH heterogeneous structure, the Rh/RhOOH metallene exhibits superior electrocatalytic performance towards hydrogen evolution reaction (HER, overpotential of 29 mV) and EG oxidation reaction (EGOR, specific activity of 1.051 mA cm –2 ). Encouragingly, in the constructed EG-assisted seawater electrolysis system, the Rh/RhOOH metallene only needs a low cell voltage of 0.678 V to achieve a current density of 10 mA cm –2 for energy-saving H 2 production, which significantly reduces energy consumption compared to conventional seawater electrolysis.
研究领域:
材料科学
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电化学
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催化科学
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DOI
高影响因子
APPLIED CATALYSIS A-GENERAL
·
2022
·
IF 5.723
Yucong Song,Xiaoshu Ding,Fang Li,Dongsheng Zhang,Xinqiang Zhao,Yanji Wang
Methylcyclohexane diisocyanate (HTDI) is the core raw material for the synthesis of high-grade polyurethane . Aiming at the problems existing environmental pollution and safety risks in the phosgene process, a novel and green synthesis route of HTDI was proposed. We studied the catalytic hydrogenation of dimethyl toluene dicarbamate (TDC) benzene ring to methyl cyclohexyldicarbamate (HTDC) in this novel route. The effects of metal active components, supports and metal Rh loadings on the catalytic performance were investigated. It was found that the supported Rh/γ-Al 2 O 3 catalyst had excellent catalytic activity and selectivity. The yield of HTDC was close to 100 % at 100 °C under 3 MPa hydrogen pressure. However, the catalyst was deactivated seriously after the reaction. The organic matter adsorbed on the catalyst surface and covered the active metal was the main reason for the catalyst deactivation . Fortunately, the deactivated catalyst could be regenerated by solvent washing and high temperature calcination .
研究领域:
化学工程
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环境科学
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产品关联
DOI
高影响因子
CATALYSIS LETTERS
·
2021
·Vol. 152
·期 7
·2164-2177
·
IF 3.186
Hu Yin,Chen Wei,Chen Yongxin,Zhang Fen,Song Weiguo,Wang Lingling,Fu Jianping,Ren Xiangrong,You Shengyong,Cao Changyan,Yu Zhonghua,Dong Xiaona
Rh/NaNbO 3 catalyst was prepared by a facile solvothermal method combined with photo-deposition technique. Over this catalyst, both conversion and selectivity were up to 100.0% in ten reaction recycles for the selective hydrogenation of benzoic acid to cyclohexane carboxylic acid at room temperature and 0.5 MPa H 2 pressure. TOF value of the catalyst was 207 h −1 for this hydrogenation reaction. The excellent performance and the mild hydrogenation conditions were among the best of the reference catalysts with different supports or surface metal active component. Multiple characterization techniques were adopted to further study the essence of the superior hydrogenation performance. It was found that the abundant oxygen vacancies and the reduction in situ of Rh species accounted for the excellent hydrogenation performance. Besides, the reducible perovskite support, small Rh species particle, specific morphology and pore structure of the catalyst also played important roles in improving the hydrogenation reaction. After eleven hydrogenation recycles, the inactivation of the catalyst was also investigated, and attributed to the carbon deposition and the leaching of Rh species during hydrogenation process. It is an attractive work to design the highly efficient catalysts for benzoic acid hydrogenation with potential application value. Graphic Abstract
研究领域:
催化
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化学工程
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材料科学
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高影响因子
JOURNAL OF CATALYSIS
·
2018
·
IF 6.759
Yuqing Wang,Li Yan,Cunyao Li,Miao Jiang,Ziang Zhao,Guangjin Hou,Yunjie Ding
Porous organic copolymer (designated as CPOL-BP&P(OPh) 3 ) containing vinyl biphephos moieties and tris(4-vinylphenyl)phosphite (P(OPh) 3 ) moieties was synthesized through a solvothermal copolymerization technique. After metalation with Rh precursor, an efficient heterogeneous catalyst Rh/CPOL-BP&P(OPh) 3 for the hydroformylation of 1-butene is presented with high activity (TOF = 2490.3 h −1 ) and regioselectivity (l:b = 40.0). The Rh/CPOL-BP&P(OPh) 3 catalyst has been investigated by using solid-state 13 C MAS NMR, in situ FT-IR spectroscopy, nitrogen sorption measurements, SEM, TEM, and XPS. Interestingly, in situ FT-IR spectra showed that Rh species tended to coordinate with both two kinds of P species from biphephos and P(OPh) 3 ligands in the Rh/CPOL-BP&P(OPh) 3 polymer frame rather than one kind of them. Therefore, the synergistic effect of three kinds of coordination compound formed between Rh species and both ligands could be responsible for the high activity and regioselectivity observed in hydroformylation of 1-butene.
研究领域:
化学工程
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催化材料科学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）