Catalysts
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2024
·Vol. 14
·期 11
·756
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IF 3.8
Xuekai Shan,Guolin Zhang,Ying Zhang,Shuobo Zhang,Fang Guo,Qi Xu
Selective CO2hydrogenation faces significant technical challenges, although many efforts have been made in this regard. Herein, a Ni-doped In2O3catalyst supported by g-C3N4was prepared using the co-precipitation method, and its composition, morphology, specific surface area, and band gap were characterized using TEM, XPS, BET, XRD, CO2-TPD, H2-TPR, UV-Vis, etc. The catalytic hydrogenation reduction of CO2to produce methanol was tested. Under low-photothermal conditions (1.0 MPa), the hydrogenation of carbon dioxide to methanol is stable, effective, and highly selective, with a spatiotemporal yield of 86.0 gMeOHh−1kgcat−1, which is 30.9% higher than that of Ni-In2O3without g-C3N4loading under the same conditions.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
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2024
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IF 8.3
Yiling Wu,Kaiji Xu,Jian Tian,Longmei Shang,Kok Bing Tan,Hao Sun,Kang Sun,Xiaoping Rao,Guowu Zhan
The efficient and economic conversion of CO2 and renewable H2 into methanol has received intensive attention due to growing concern for anthropogenic CO2 emissions, particularly from fossil fuel combustion. Herein, we have developed a novel method for preparing Ni/In2O3 nanocatalysts by using porous MIL-68(In) and nickel(II) acetylacetonate (Ni(acac)2) as the dual precursors of In2O3 and Ni components, respectively. Combined with in-depth characterization analysis, it was revealed that the utilization of MIL-68(In) as precursors favored the good distribution of Ni nanoparticles (∼6.2 nm) on the porous In2O3 support and inhibited the metal sintering at high temperatures. The varied catalyst fabrication parameters were explored, indicating that the designed Ni/In2O3 catalyst (Ni content of 5 wt %) exhibited better catalytic performance than the compared catalyst prepared using In(OH)3 as a precursor of In2O3. The obtained Ni/In2O3 catalyst also showed excellent durability in long-term tests (120 h). However, a high Ni loading (31 wt %) would result in the formation of the Ni-In alloy phase during the CO2 hydrogenation which favored CO formation with selectivity as high as 69%. This phenomenon is more obvious if Ni and In2O3 had a strong interaction, depending on the catalyst fabrication methods. In addition, with the aid of in situ diffuse reflectance infrared Fourier transform spectroscopy and density functional theory (DFT) calculations, the Ni/In2O3 catalyst predominantly follows the formate pathway in the CO2 hydrogenation to methanol, with HCOO* and *H3CO as the major intermediates, while the small size of Ni particles is beneficial to the formation of formate species based on DFT calculation. This study suggests that the Ni/In2O3 nanocatalyst fabricated using metal–organic frameworks as precursors can effectively promote CO2 thermal hydrogenation to methanol.
研究领域:
催化化学
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材料科学
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环境科学
✓ 已验证
DOI
PubMed
高影响因子
ACS Catalysis
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2024
·
IF 11.3
Yanmei Cai,Cunbiao Lin,Xingwen Cha,Yiling Wu,Xiaoping Rao,Kok Bing Tan,Dongren Cai,Gui-Lin Zhuang,Guowu Zhan
The supported Ni/In2O3 catalysts are of great interest in CO2 hydrogenation, but the formation of the In0 or Ni–In alloy phases due to over-reduction would lead to rapid catalyst deactivation. Herein, thin Al2O3 films were deposited on the Ni/In2O3 surface by atomic layer deposition (ALD) as an antireduction agent, which enables the In2O3 catalyst to maintain a significant abundance of active In3+ species even during high-temperature H2 treatment (400 °C, 2 h), thereby effectively resisting the deactivation caused by over-reduction of In2O3. Various characterization methods confirm the antiover-reduction effect of ALD-Al2O3 films, namely, inhibiting the formation of In0 and In3Ni2 alloys during high-temperature H2 treatment and facilitating the reoxidation of low-valence In to form the active In2O3–x phase in the presence of a CO2 atmosphere. As treated with H2 at 400 °C, the 5Al2O3/Ni/In2O3-R400 catalyst exhibited an STYMeOH of 7.39 gMeOH h–1gNi–1 and a methanol selectivity of 64% (reaction conditions: 3 MPa, 300 °C, and 12,000 mL gcat–1h–1). Particularly, the STYMeOH increased by 11.5 times as compared with that of the Ni/In2O3-R400 catalyst without coating the ALD-Al2O3 layer (0.59 gMeOH h–1gNi–1). Density functional theory (DFT) calculations validate the effectiveness of specific charge transfer tendencies in suppressing the over-reduction of high-valence In species. Through the analysis of the crystal orbital Hamilton population (COHP) and projected density of states (PDOS) electronic structures of the adsorbate species, the Al2O3/Ni/In2O3 catalyst is shown to significantly enhance CO2 activation and further catalytic reactions. Accordingly, this study unveils the deactivation mechanism of In2O3-based catalysts due to over-reduction and provides a method to regulate their reduction level by depositing ALD-Al2O3 films on the In2O3-based catalysts.
研究领域:
催化化学
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材料科学
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理论计算化学
✓ 已验证
产品关联
DOI
高影响因子
ENERGY & FUELS
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2023
·
IF 5.3
Wenqi Li,Yongli Shen,Linxiu Dai,Changhua An
Rational design of highly efficient catalysts for the dehydrogenation of ammonia borane (AB) to produce hydrogen is still challenging. The size and shape effects of catalysts on the performance have been well documented in the past decades. Nevertheless, there is still much space for study on the crystal structure-dependent catalytic performance. Herein, In2O3-supported hexagonal-close-packed (hcp) Ni (hcp-Ni/In2O3) has been prepared via impregnation of corresponding nanoparticles onto In2O3. The stronger electronic metal–support interaction in hcp-Ni/In2O3 than in fcc-Ni/In2O3 endows it with high capacity to activate AB molecules. It exhibits excellent hydrogen evolution activity from catalytic dehydrogenation of AB with a rate of 7.5 molH2 mol–1Ni min–1, which is 1.7 times that of the supported fcc sample. The systematic experiments and DFT calculations demonstrate that the hcp catalyst possesses stronger hydrophilicity and lower activation energy for the dissociation of H2O than the fcc counterpart. Moreover, the assistance with sonication enhances the process of mass and heat transfer and accelerates the reaction. This work provides a new way for the achievement of efficient metastable catalytic systems and promotes the construction of advanced devices toward various applications.
研究领域:
材料科学
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催化
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化学工程
·
物理化学
✓ 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）