CHEMICAL ENGINEERING SCIENCE
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2026
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IF 5.1
Chaoran He,Shanshan Zhao,Jiafei Lyu,Bofeng Zhang,Rongrong Zhang,Guozhu Liu
The severe carbon deposition that plagues conventional Ni catalysts in dry reforming of methane (DRM) originates from the kinetic mismatch between CH 4 cracking and CO 2 dissociation. Here, we design an atomically thin Sm-doped MgAlO x overlayer to encapsulate Ni nanoparticles, creating a confined reaction environment that intrinsically couples these two critical steps. The Sm-induced electron donation to Ni accelerates CH 4 dissociation by weakening the C-H bonds, while the Sm-doped thin overlayer with rich oxygen vacancies facilitates the rapid decomposition of CO 2 -derived carbonate intermediates (m-CO 3 2− ) and shortens the diffusion path for the resultant active oxygen species to gasify surface cavrbon precursors. The optimized catalyst achieves high conversions of CH 4 (91.0%) and CO 2 (94.0%) at 800 °C, reducing carbon deposition from 39.47% to 9.50%, and maintains stable performance over 100 h. This work demonstrates that precise reducible-oxide overlayers engineering can intrinsically align reaction kinetics to break the classical deactivation cycle of Ni-based catalysts in DRM.
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DOI
高影响因子
FUEL
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2022
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IF 8.035
Zhiliang Ou,Jingyu Ran,Huayu Qiu,Xin Huang,Changlei Qin
The acidity and basicity of Ni based catalysts play very important role in the catalytic performance during dry reforming of methane. Hence, the effects of surface basicity regulated by adding the oxides (CaO, MgO, ZnO and La 2 O 3 ) in Ni/CeO 2 catalysts on the catalytic behavior were systematically investigated, and the characterization methods and DFT calculations were performed to reveal the underlying mechanism. It was found that the addition of basic oxides could improve the activity and stability due to these oxides could increase the adsorbed oxygen, reduce the size of Ni particle and improve the interaction between Ni and support, in particular, the MgO interacts with Ni to form MgNiO 2 spinel, which contribute to promote Ni dispersion and inhibit Ni aggregation. Moreover, the results suggested that the resistance to carbon deposition has something to do with the surface basicity. To a certain degree, the increasing the amount of basic site and enhancing alkaline strength could suppress the carbon deposition of Ni based catalysts. This is mainly because that the basic site is beneficial to CO 2 adsorption and activation based the DFT calculations, which could accelerate the elimination of carbon deposition by provide more oxygen species. These results could provide some useful information to the design and synthesis of Ni-based catalysts.
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
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2022
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IF 7.139
Xiaodi Zhang,Ying Xu,Guojie Zhang,Chenlei Wu,Jun Liu,Yongkang Lv
Nitrogen (N)-doped carbon materials have become promising candidates for many applications. In this paper, the biomass activated carbon (BC) was obtained by carbonization and activation of soybean meal. Using soybean meal as the precursor, potassium hydroxide (KOH) as the activator and melamine as the nitrogen source, a series of N-doped porous biomass carbons (H-NC-X) with different N contents were achieved via a facile post-treatment nitrogen doping strategy. Then these samples were used as a catalyst for dry reforming of methane (DRM) reaction and an adsorbent for CO 2 capture. Among all the investigated samples, BC has the largest specific surface area and the best pore structure characteristics, showing the best CO 2 adsorption capacity . However, when BC was used as a catalyst for DRM reaction, it showed the worst catalytic performance. After nitrogen doping treatment, the CO 2 adsorption capacity of the prepared N-doped biomass porous carbon decreased gradually with the increase of the introduced N content. This is mainly due to the destruction of the microporous structure of porous carbon by post-processing nitrogen doping. In contrast, when nitrogen-doped porous carbon was used as the reforming catalyst, the catalytic activity increased with the increase of the introduced N content. The order was: H-NC-30>H-NC-20>H-NC-10. This indicates that when nitrogen-doped porous carbon was used as an adsorbent, the pore structure plays a major role; while when it was used as a reforming catalyst, nitrogen functional groups are the major active sites. This study provides a promising N-doped carbon material for effect CO 2 adsorption and DRM reactions.
研究领域:
材料科学
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环境科学
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DOI
高影响因子
NEW JOURNAL OF CHEMISTRY
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2026
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IF 2.6
Jiming Wang,Min Ji,Min Wang
The integration of photocatalysis and thermal catalysis offers a sustainable route to drive the dry reforming of methane (DRM) at low temperatures, addressing the high energy consumption of traditional thermocatalytic processes. Herein, we systematically explore the effects of doping rare earth elements (Ce, Pr, and Y) on the photothermal catalytic activity and stability of Ni-based catalysts (Ni–MOx–Al2O3) for DRM. Results demonstrate that Ce doping significantly enhances charge carrier separation efficiency and reduces interfacial impedance, endowing Ni–Ce–Al with superior photocatalytic activity compared to Ni–Pr–Al and Ni–Y–Al catalysts. After 100 h of continuous reaction at 650 °C, the conversions of CH4 and CO2 only decrease from 59.0% and 62.0% to 52.6% and 56.8%, respectively. Mechanistic studies reveal that Ce incorporation increases the density of surface oxygen vacancies, which promotes the activation of CH4 and CO2 and enhances coke resistance under light conditions. Kinetic analysis confirms that Ni–Ce–Al possesses the lowest activation energies for CH4 (40.6 kJ mol−1) and CO2 (36.7 kJ mol−1) dissociation under illumination. This work provides helpful guidance for the design of high-performance Ni-based photothermal catalysts for DRM through rare earth modification, highlighting the crucial role of Ce in optimizing electronic properties and anti-coking ability.
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DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2023
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IF 7.2
Yajing Cai,Guojie Zhang,Jun Liu,Yunfei Zhang,Tianshan Li,Xiaodi Zhang,Ying Wang,Yuqiong Zhao,Guoqiang Li
Dry reforming of methane (DRM) is an effective method for achieving carbon reduction and carbon neutrality by directly converting two greenhouse gases , CH 4 and CO 2 , into value-added products. However, catalysts used in this process are prone to metal sintering and carbon deposition , which are major obstacles. Thus, the design of high-performance catalysts is crucial for the success of dry reforming technology. In this paper, a series of Co-based catalysts modified with different rare earth metals (Y, Tb, Gd) and γ-Al 2 O 3 as the support were prepared using the conventional co-impregnation method. The effects of the introduction of rare earth metals additives on the activity and resistance to carbon build-up of the catalysts were investigated. The catalysts were analyzed using various characterization techniques. The results showed that Y and Tb as additives could effectively improve the activity and stability of the catalyst. However, the Gd modified Co-based catalyst had a large specific surface area but was less favorable for the DRM reaction. The best performance catalyst was achieved with the 10Co–5Y/γ-Al 2 O 3 under 750 °C with CH 4 and CO 2 conversions of 91.79% and 98.33%, respectively. This is mainly due to the fact that the introduction of Y enhances the electron transfer between Co and metal oxides , generating more oxygen vacancies and base vacancies on the surface, thus enhancing the adsorption and activation of CO 2 . The 10Co–5Y/γ-Al 2 O 3 catalyst demonstrated excellent DRM performance even after 20 h at 750 °C. Moreover, we proposed a hypothesis regarding the mechanism of resistance to carbon build-up. This study provides a reasonable idea to design Co-based catalysts with resistance to sintering and carbon accumulation to improve the performance of reforming catalysts.
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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环境科学
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DOI
高影响因子
CHEMICAL ENGINEERING SCIENCE
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2024
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IF 4.1
Yanan Li,Yuqi Wang,Jinlei Wu,Shuqin Gao,Binjing Zhu,Junqian Wang,Jing Zhao,Le Wu,Lan Zheng,Xiaoli Zhang
Dry reforming of methane (DRM) is considered one of the most efficient methods for carbon utilization, as it can transform greenhouse gases (CH 4 and CO 2 ) into syngas (CO and H 2 ) which could be widely used in the production of high-value hydrocarbons. The synergistic effect between Ni and Co is leveraged to enhance the coke resistance and stability of Ni-based catalyst during the DRM process, building upon the surface spatial confinement provided by honeycomb-lantern-like CeO 2 support. The enhanced catalytic performance of Ni 0.9 Co 0.1 catalyst can be attributed primarily to the addition of cobalt, which facilitates CO 2 adsorption and activation, further promotes the Boudouard reaction and aids in the elimination of coke. This phenomenon is supported by evidence from CO 2 -TPD, XPS, SEM, TGA, XRD, and CO 2 -TPO analyses. Furthermore, the kinetics of Ni 0.9 Co 0.1 are examined using Power-Law (PL) and Langmuir-Hinshelwood (LH) mechanisms, obtaining the explicit equations for the rate constants ( k and k r ), reaction orders of the reactants (α and β), and adsorption equilibrium constants ( K CH 4 and K CO 2 ). The comparison of the predicted CH 4 consumption rates with the experimental rates suggests that the LH mechanism is notably more precise than PL mechanism for Ni 0.9 Co 0.1 catalyst. Moreover, the relevant kinetic parameters (the activation energy and pre-exponential factor), pertinent to coke gasification process for the spent Ni 0.9 Co 0.1 and Ni 1.0 , are determined and calculated through CO 2 -TPO characterization and the modified Wigner-Polanyi equation.
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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环境科学
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产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
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2021
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IF 5.816
Sheng Li,Guojie Zhang,Jiming Wang,Jun Liu,Yongkang Lv
Carbon materials are widely used as catalysts or supports due to their excellent properties. In this paper, the tungsten carbide-activated carbon (WC-AC) composite support was successfully prepared by in-situ carburizing on AC matrix, which is characterized by the covalent anchoring of WC on the AC support. The active metal Co was supported on WC-AC for dry reforming of methane (DRM). Samples were analyzed by N 2 physisorption measurements, XRD , XPS , H 2 -TPR, H 2 -TPD, CH 4 &CO 2 -TPSR, TG-DTG. The WC-AC stabilizes the disturbance of C in AC, alleviates the gasification effect of CO 2 and increases the active sites for CH 4 cracking. Moreover, WC provides a resistance-less bridge suitable for the Co 3+ → Co 2+ , resulting in a high Co 2+ /Co 3+ ratio on the catalyst surface . This enhances the interaction between the Co species and the WC-AC, thereby enhancing the CH 4 activation. In the process of WC-AC promoting Co 3+ →Co 2+ , the catalyst surface is accompanied by the generation of oxygen vacancies . This can enhance the dissociative adsorption of CO 2 on surface of the WC-cobalt oxide, and at the same time increase the relative proportion of adsorbed oxygen on the catalyst surface, thereby effectively inhibiting the formation of coke. However, the small amount of graphitic carbon generated due to the strong coupling of WC and Co is the main reason for deactivation of Co/WC-AC.
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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DOI
高影响因子
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