Catalysis Science & Technology
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2024
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IF 4.4
Ning Huang,Yue Ma,Boyang Liu,Letong Yang,Xiaocheng Lan,Xiaodong Wu,Tiefeng Wang
An approach to the design of a Rh-based bimetallic catalyst for ethylene hydroformylation was introduced. Among late 3d transition metals (Fe, Co, Ni, Cu and Zn), the thermodynamic feasibility of alloying with Rh was evaluated using phase diagram, with Cu excluded from consideration. The reducibility of oxide precursor to form an alloy with Rh was examined by H2 temperature-programmed reduction (H2-TPR), further excluding Fe and Zn from the potential alloying elements. Density functional theory (DFT) calculations were employed to select descriptors for catalytic performance, suggesting that a lower CO adsorption energy would enhance hydroformylation activity, and a larger difference between CO and H adsorption energies would promote selectivity to aldehydes and alcohols (oxy selectivity), suggesting that Co would be a better alloying element than Ni. As predicted, a RhCo bimetallic catalyst was successfully synthesized, which showed the highest oxy yield in ethylene hydroformylation among all the bimetallic catalysts, with a superior selectivity compared to a monometallic Rh catalyst.
研究领域:
催化化学
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材料科学
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理论计算
✓ 已验证
产品关联
DOI
高影响因子
Inorganic Chemistry Frontiers
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2024
·Vol. 12
·期 1
·217-230
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IF 6.1
Jinggao Wu,Canyu Zhong,Xiaofan Chen,Jing Huang
Li3V2(PO4)3 (LVP) coated with N and S co-doped carbon (NSC) was investigated by DFT calculation, suggesting that NSC significantly enhances electronic conductivity and lowers the energy barrier to Li+ migration in comparison to LVP-embedded in pristine carbon. To experimentally confirm the theoretical prediction, three types of LVP particle embedded in N and S co-doped porous carbon (LVP@NSC) materials with various nitrogen and sulfur molar ratios (N : S = 1 : 1, 1 : 2 and 2 : 1) were prepared by a facile freeze-drying-assisted wet chemical route associated with a post-annealing process. When used as a cathode for a lithium-ion battery (LIB), the designed LVP@NSC with N : S = 1 : 2 exhibits outstanding high rate capacities of 124.4 and 107.85 mA h g−1, respectively, at 2 and 20 C in a voltage window of 3.0–4.3 V, and an ultralong cycling stability of 500 times at 20 C while retaining a reversible capacity of 100.22 mA h g−1, possibly due to its smallest charge transfer resistance and highest Li+ migration coefficient, which is in good agreement with the theoretical prediction. This work not only reveals the critical role of an interaction mechanism between NSC and LVP, but also offers great potential for high-energy density LIB applications.
研究领域:
材料科学
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电化学
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计算化学
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DOI
高影响因子
Science China-Chemistry
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2024
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IF 10.4
Wu Shuang-Xue,Dong Yu-Jiao,Yang Yang,Qin Chao,Sun Chun-Yi,Guan Wei,Wang Xin-Long,Su Zhong-Min
Combining theoretical prediction and experimental exploration, the first sandwich-type polyoxovanadoborate (POVB) with an odd number of nuclei, [V 11 B 26 O 73 (OH) 10 ] 8− (1), was discovered under hydrothermal conditions. Density-functional theory (DFT) gives a rationalization for the existence of this structure and the structural feature is consistent with the {V N B 2N+X } (X = 2, 4, 6, 8) general formula. Excitingly, when Co and 1,10-phenanthroline (phen) are introduced into the synthesis of vanadoborates system, a 100-nuclei [Co 6 (phen) 10 (H 2 O) 8 ][V 14 Co 12 B 72 O 144 (OH) 20 ]·28H 2 O (2) and a 102-nuclei [Co 6 (phen) 14 (H 2 O) 4 ][V 14 Co 12 B 72 O 144 (OH) 20 ]·23H 2 O (3) with the same core structure of [V 14 Co 12 B 72 ] 12− are obtained. The vase-shaped [V 14 Co 12 B 72 ] polyanion is a multilayered sandwich-type structure containing seven distinct structural layers and is the largest known POVB. Furthermore, 2 demonstrates exceptional thermal and chemical stability and serves as an efficient and stable catalyst for the photoreduction of carbon dioxide.
研究领域:
材料化学
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理论化学
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催化化学
✓ 已验证
产品关联
DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
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2022
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IF 16.744
Xiaoxiao Li,Yu Yan,Xiaonan Zheng,Yuan Yao,Yang Liu
Single atom catalysts (SACs) exhibit impressive catalytic activity for various reactions due to low coordination environment and tunable electronic structures, attracting increasing attention. However, it is big challenge to develop transition-metal-based SACs for oxygen reduction reaction (ORR) with high stability. Bioinspired by the structure and mechanism of vanadium-dependent haloperoxidase, we herein demonstrate that saturated coordination could boost ORR activity of atomically dispersed V-N-C catalyst combining DFT prediction and experimental verification. Spontaneous axial OH coordination to V-N-C catalyst in alkaline electrolyte not only optimizes the adsorption interaction for key intermediates to boost ORR activity, but also keeps vanadium atom at the highest valence against Fenton activity to improve the stability. The as-designed catalyst exhibits half-wave potential of 0.858 V vs . RHE for ORR, comparable to the commercial Pt/C benchmark. This work provides a proof-of-concept design of SACs and broadens the horizon of its potential applications.
研究领域:
电化学
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催化材料
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理论计算
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能源材料
✓ 已验证
DOI
高影响因子
危险品化学品经营许可证（带存储）