Nature Communications
·
2023
·Vol. 14
·期 1
·1-12
·
IF 16.6
Mao Qiqi,Mu Xu,Wang Wenxin,Deng Kai,Yu Hongjie,Wang Ziqiang,Xu You,Wang Liang,Wang Hongjing
Organic electrocatalytic conversion is an essential pathway for the green conversion of low-cost organic compounds to high-value chemicals, which urgently demands the development of efficient electrocatalysts. Here, we report a Cu single-atom dispersed Rh metallene arrays on Cu foam for cathodic nitrobenzene electroreduction reaction and anodic methanol oxidation reaction. In the coupled electrocatalytic system, the Cu single-atom -Rh metallene arrays on Cu foam requires only the low voltages of 1.18 V to reach current densities of 100 mA cm −2 for generating aniline and formate, with up to ~100% of nitrobenzene conversion/ aniline selectivity and over ~90% of formate Faraday efficiency, achieving synthesis of high-value chemicals. Density functional theory calculations reveal the electron effect between Cu single-atom and Rh host and catalytic reaction mechanism. The synergistic catalytic effect and H*-spillover effect can improve catalytic reaction process and reduce energy barrier for reaction process, thus enhancing electrocatalytic reaction activity and target product selectivity.
研究领域:
化学工程
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电化学
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催化
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材料科学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF HAZARDOUS MATERIALS
·
2014
·
IF 4.331
Yanlin Ren,Guangyin Fan,Chenyu Wang
Reduced graphene oxide (RGO) supported rhodium nanoparticles (Rh-NPs/RGO) was synthesized through one-pot polyol co-reduction of graphene oxide (GO) and rhodium chloride. The catalytic property of Rh-NPs/RGO was investigated for the aqueous phase hydrodechlorination (HDC) of 4-chlorophenol (4-CP). A complete conversion of 4-CP into high valued products of cyclohexanone (selectivity: 23.2%) and cyclohexanol (selectivity: 76.8%) was successfully achieved at 303 K and balloon hydrogen pressure in a short reaction time of 50 min when 1.5 g/L of 4-CP was introduced. By comparing with Rh-NPs deposited on the other supports, Rh-NPs/RGO delivered the highest initial rate (111.4 mmol/g Rh min) for 4-CP HDC reaction under the identical conditions. The substantial catalytic activity of Rh-NPs/RGO can be ascribed to the small and uniform particle size of Rh (average particle size was 1.7 ± 0.14 nm) on the surface of the RGO sheets and an electron-deficient state of Rh in the catalyst as a result of the strong interaction between the active sites and the surface function groups of RGO.
研究领域:
催化
·
环境化学
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材料科学
✓ 已验证
产品关联
DOI
PubMed
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
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材料化学
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有机合成
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多相催化
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功能材料
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工业化学
✓ 已验证
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2025
·
IF 8.2
Kaiting Chen,Qingwei Li,Xinyu Han,Cheng Rao,Xiangguang Yang,Yibo Zhang
Developing efficient low-temperature selective catalytic reduction (CO-SCR) catalysts remains a key challenge in reducing nitrogen oxide (NOx) emissions. Here, we report a photothermal-enhanced Rh–Mn/CoAlOx heterostructure catalyst that achieves excellent NO conversion (more than 90% at 140 °C) and N2 selectivity (>80%) under visible to infrared light irradiation. By integration of highly dispersed Rh units with Mn clusters onto a hydrotalcite-derived CoAlOx support, the catalyst exhibits synergistic light absorption and dynamic lattice oxygen migration capabilities. Through combined analysis using in situ DRIFTS, XAFS, XPS, EPR, and other techniques, we reveal that Mn doping induces numerous oxygen vacancies and promotes electron transfer between Rh and Mn, facilitating lattice oxygen activation via a mechanism similar to the Mars-van Krevelen mechanism. Light exposure reduces the activation energy and, according to Arrhenius analysis and NO-TPD results, accelerates the decomposition of nitrate intermediates and enhances the conversion rate of nitrous oxide to N2. Density functional theory (DFT) calculations confirm that N2O is more likely to be generated at the Rh–Mn interface, demonstrating its enhanced low-temperature activation ability for NO. This study innovatively enhances the catalytic performance of CO-SCR using light, providing a sustainable method for reducing low-energy NOx emissions.
研究领域:
催化
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环境化学
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材料科学
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物理化学
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纳米技术
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化学反应工程
✓ 已验证
产品关联
DOI
PubMed
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2022
·
IF 7.139
Rongfei Wang,Xiaodeng Wang,Min Cheng,Yunpeng Wei,Jihong Xia,Hua Lin,Wei Sun,Weihua Hu
A wide diversity of phosphides of platinum-group metal including Rh, Ru and Ir exhibit intriguing electrocatalytic activity toward hydrogen evolution reaction (HER). The phosphidation degree, namely the P dosage in these phosphides shows pronounced influence on the catalytic performance but is hard to control. In this work we developed a reliable strategy to synthesize Rh 2 P-based nanoparticles with controlled phosphidation degree, and investigated the influence of phosphidation degree on HER. It is found that the heterostructured Rh 2 P/Rh nanoparticle, i.e., the P-deficient composite with mixed metallic and phosphide phases, outperforms either the metallic Rh or pure Rh 2 P nanoparticles. As-synthesized Rh 2 P/Rh nanoparticles supported on P/N co-doped graphene (denoted as Rh 2 P/Rh-G) display remarkable HER activity with tiny overpotential of 17 and 19 mV at 10 mA cm −2 current density in alkaline and acid, efficiently surpassing its Rh-based rivals and benchmark Pt/C catalyst. Meanwhile it illustrates a large mass-specific activity (3.23 and 6.26 A mg −1 @50 mV overpotential in alkaline and acid, respectively) due to its high activity and low metal loading. Density functional theory (DFT) calculation indicates that the Rh 2 P/Rh heterostructured interface possesses the optimal close-to-zero value of hydrogen adsorption energy and water dissociation process is accelerated, and thus boosts HER activity.
研究领域:
材料科学
·
电化学
·
纳米技术
·
催化
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2024
·
IF 8.1
Cengceng Du,Zhenyu Wang,Xin Chen,Yiming Wang,Chen Chen,Xinyu Liu,Yuqiu Huo,Hongbin Sun,Guangwen Xu
The efficient and high-quality production for hydrogen through water electrolysis at high current densities is crucial for commercial utilization. However, the performance of existing hydrogen evolution reaction (HER) electrocatalysts is far from satisfactory. In this regard, we proposed a method to prepare Rh–Ni(OH) 2 catalyst based on Nickel foam (NF). The hydrolysis galvanic replacement of nickel boride with RhCl 3 led to produce a lattice contraction in Ni(OH) 2 due to the rigid pressure generated, resulting in outstanding HER performance at high current densities. It achieves an industrial current density of 500 mA cm −2 with an overpotential of 130 mV. Furthermore, at the industrially prefer temperature of 80 °C, only 67 mV overpotential is required. The catalyst also demonstrated exceptional stability, maintaining excellent performance even after a stability test of 100 days with a current density of 200 mA cm −2 . Through Density-functional theory (DFT) calculations, Rh series reduced the hydrogen adsorption free energy.
研究领域:
电化学
·
材料科学
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催化
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能源存储与转换
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2022
·
IF 10.383
Weiwei Li,Chunhua Zhang,Ziman Zheng,Xiaoyu Zhang,Lin Zhang,Alexander Kuhn
Electrochemical regeneration of the reduced form of the nicotinamide adenine dinucleotide (NADH) cofactor catalyzed by immobilized [Rh(Cp*)(bpy)Cl]+ is a promising approach for the enzymatic synthesis of many valuable chemicals with NAD-dependent dehydrogenases. However, rational control of the efficiency is often limited by the irregular structure of the electrode/electrolyte interface and the accessibility of the molecular catalyst. Here, we propose an electrochemical system for NADH cofactor regeneration, based on highly ordered three- dimensional (3D) metal–organic framework (NU-1000) films. [Rh(Cp*)(bpy)Cl]+ is incorporated at the zirconium nodes of NU-1000 via solvent-assisted ligand incorporation (SALI), leading to a diffusion-controlled behavior, associated with an electron hopping mechanism. Varying the ratio of redox-active [Rh(Cp*)(bpy)Cl]+ and inactive postgrafting agents enables the elaboration of functional electrodes with tunable electrocatalytic activity for NADH regeneration. The exceptionally high faradic efficiency of 97%, associated with a very high turnover frequency (TOF) of ∼1400 h–1 for NADH regeneration, and the total turnover number (TTN) of over 20000 for the enzymatic conversion from pyruvate to l-lactate, when coupled with l-lactate dehydrogenases (LDH) as a model reaction, open up promising perspectives for employing these electrodes in various alternative bioelectrosynthesis approaches.
研究领域:
电化学
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催化
·
生物电化学
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材料科学
✓ 已验证
DOI
PubMed
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2022
·
IF 4.326
Mingyue Zhang,Jianguo Liu,Bo Yang,Longlong Ma,Nan Wang,Xiuzhi Wei
The development of transition-metal heterogeneous catalysts for economical and effective synthesis of N-methylamine, especially for the monomethylation of amines, is still challenging. Herein, two Rh-supported covalent organic framework (COF) heterogeneous catalysts Rh/MelCOF were facile-synthesized by a Schiff base reaction using melamine as a precursor, and, for the first time, it was successfully applied to the effective and high selective tandem reaction of transfer hydrogenation and monomethylation of nitroaromatic hydrocarbons, with methanol as a C1 and hydrogenation source. A series of nitroaromatic hydrocarbons, including heterocyclic or sterically hindered derivatives, can be well tolerated, and the catalyst could also be reused four times without losing significant reactivity. At the same time, the study of the Rh/MelCOF mechanism supports the hydrogen-borrowing mechanism and puts forward the reaction pathway of azobenzene as an intermediate, which is better than the hydrogen-transfer pathway from N-phenylhydroxylamine to aniline directly. This work expands the application of COF catalysts and provides an effective way to obtain mono-N-methylated amines from nitroaromatic hydrocarbons, as well as the detailed mechanism of Rh/COF-catalyzed tandem transfer hydrogenation and monomethylation of amines.
研究领域:
催化
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有机化学
·
材料科学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2021
·
IF 13.273
Junlin Cai,Xinyan Liao,Pingting Li,Qiuxiang Wang,Hongpu Huang,Zixi Lyu,Jing Lin,Shuifen Xie
Surface defects on electrocatalysts can effectively reduce reaction barriers and facilitate the kinetics of hydrogen evolution and oxidation reactions (HER/HOR). However, precisely engineering such surface structures remains a significant challenge. Herein, penta-twinned (PTw) Rh@Pt x core–shell nanobranches (NBs) with intense surface strains were facilely synthesized using PTw Rh NBs as the seeds for overgrowth of active Pt-shells. Through precisely regulating the supply of Pt precursor solution via a micro-syringe pump, the ultrathin Pt-shells conform to and replicate the twin defects of the PTw Rh seeds. Significantly, the shell thickness can be precisely controlled from 1.0, 2.0, and 3.8 to 5.0 atomic layers. Due to the integration of surface twinned defects, compressive strain and the core–shell ligand effect, these Rh@Pt x NBs exhibit superior hydrogen redox electrocatalytic performance compared to state-of-the-art Pt/C. Among the prepared materials, the Rh@Pt 0.83 NBs with a 3.8 atomic layer Pt-shell showed the highest mass activity (2.36 A mg Pt −1 ) and specific activity (6.55 mA cm −2 ) for HER at –0.07 V and presented the lowest overpotential (44 mV) at 10 mA cm −2 , less than half the overpotential of the commercial Pt/C (98 mV). In terms of HOR, the Rh@Pt 0.83 NBs showed a superior exchange current density (1.97 mA cm −2 ), approximately 7 times higher than that of Pt/C. Our work provides a facile method to synchronously engineer the Pt-shell thickness and surface defects of Rh@Pt core–shell nanocatalysts for the creation of robust and bifunctional hydrogen redox electrocatalysts.
研究领域:
材料科学
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电化学
·
纳米技术
✓ 已验证
产品关联
DOI
高影响因子
Nanoscale Advances
·
2019
·Vol. 1
·期 10
·3941-3947
·
IF 0
Xiao Li,Yucong Yan,Yi Jiang,Xingqiao Wu,Shi Li,Jingbo Huang,Junjie Li,Yangfan Lin,Deren Yang,Hui Zhang
Hydrolysis of ammonia borane (AB) is a safe and convenient means of H2 production when efficient catalysts are used. Here we report a facile one-pot solvothermal method to synthesize Rh/WO3−x hybrid nanowires. Ultra-small Rh nanoparticles with an average size of ∼1.7 nm were tightly anchored on WO3−x nanowires. Rh/WO3−x catalysts exhibited substantially enhanced activity for hydrolytic dehydrogenation of AB under both dark and visible light irradiation conditions relative to mixed Rh nanoparticles and WO3−x nanowires (Rh + WO3−x), and Rh/C and WO3−x nanowires. X-ray photoelectron spectroscopy (XPS) analysis indicated that the synergistic effect between Rh nanoparticles and WO3−x nanowires was responsible for such an enhancement in activity. Specifically, Rh/WO3−x achieved the highest turnover frequency (TOF) with a value of 805.0 molH2 molRh−1 min−1 at room temperature under visible light irradiation. The H2 release rate as a function of reaction time exhibited a volcano plot under visible light irradiation, indicating that a self-activation process occurred in the hydrolytic dehydrogenation of AB due to additional oxygen vacancies arising from in situ reduction of WO3−x nanowires by AB, and thus an enhanced localized surface plasmon resonance (LSPR). Such a self-activation process was responsible for the enhanced catalytic activity under visible light irradiation relative to that under dark conditions, which was supported by the lower activation energy (45.2 vs. 50.5 kJ mol−1). In addition, Rh/WO3−x catalysts were relatively stable with only little loss in activity after five cycles due to the tight attachment between two components.
研究领域:
催化
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材料科学
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纳米技术
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化学工程
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光化学
✓ 已验证
产品关联
DOI
PubMed
Cell Reports Physical Science
·
2026
·Vol. 7
·期 2
·
IF 6.9
Si-Yuan Mu,Ya-Xiong Luo,Hao-Hui Xie,Ying-Zhen Ren,Yue Lou,Wen-Chao Zhang,Yong-Xing Tang,Peng-Fei Cui
The discovery of chemical bonds propels scientific advancement, and a thorough understanding of bond properties is essential for analyzing reactions and designing molecular architectures. In this work, we systematically investigate the stabilization mechanism of metalloradicals and find that, compared with benzene rings and methyl groups, the pyridyl group with electron-withdrawing properties facilitates the formation of metalloradicals. Additionally, the metalloradical could be further transformed into a dinuclear complex and then formed the first example of a Rh⋅Rh one-electron σ-bond through single-electron oxidation. Interestingly, the Rh⋅Rh one-electron σ-bond-bearing complex could revert to the original dinuclear complex under the reaction with tert -butyl isocyanide. This work considerably expands the diversity of one-electron σ-bond-bearing complexes, bridging the gap between theoretical predictions and experimental validation of Rh⋅Rh one-electron σ-bonds and demonstrating the unique ability of carborane-based ligands to stabilize unconventional bonding architectures.
✓ 已验证
DOI
高影响因子
ChemCatChem
·
2024
·
IF 3.8
Qi Yang,Ying Zheng,Yi Feng,Jie Ding,Maoshuai Li,Shouying Huang,Mei-Yan Wang,Xinbin Ma
Graphical Synergy between Rh 0 and Rh + on the Rh clusters is essential to catalyze heterogeneous formaldehyde hydroformylation. Rh 0 works as the adsorption/activation site for formaldehyde and hydrogen. Rh + works as the coordination site for CO and PPh 3 . The formed Rh─CH 2 OH* intermediate is responsible for the highly selective hydroformylation to glycolaldehyde. Controlling the metal geometric and electronic structure is of significance in developing efficient catalysts for heterogeneous hydroformylation. This study examines the structural sizes of Rh and Rh + -Rh 0 distribution to construct a highly active catalyst for formaldehyde hydroformylation. The active sites for hydroformylation require several Rh n atoms, while single-atom Rh can solely catalyze hydrogenation. The highest activity was achieved on Rh nanoclusters (0.95 nm), giving a TOF of 191 h −1 and selectivity of 82% for glycolaldehyde formation. The tunability of the electronic properties of Rh nanoclusters and the synergistic interaction between Rh + and Rh 0 are essential for enhanced activity. Pseudo- in situ FT-IR analysis elucidated that formaldehyde adsorbed on Rh nanocluster prefers to produce glycolaldehyde via hydroformylation, while formaldehyde adsorbed on isolated Rh δ+ sites tends to form methanol via hydrogenation. This study provides a new insight into the design of heterogeneous catalysts and guidance for understanding the reaction mechanism for aldehydes/olefins hydroformylation.
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
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