FUEL
·
2024
·
IF 6.7
Bin Fu,Yuqiong Zhao,Shipeng Zhang,Ying Wang,Jun Liu,Guojie Zhang
Nickel-based catalysts frequently encounter significant challenges in achieving both high CO 2 conversion and superior CO selectivity during reverse water gas shift (RWGS) reactions. To address this issue, we developed a facile strategy to prepare highly dispersed Ni/CeO 2 catalysts by forming Ce 1−x Ni x O 2−y solid solutions. Under conditions of 300–600 °C, 0.1 MPa, and a gas hourly space velocity (GHSV) of 40,000 mL g cat −1 h −1 , the 5Ni/CeO 2 -A catalyst exhibited outstanding selectivity, approaching 100 %. The RWGS reaction rate reached 1332 μmol CO g Ni −1 s −1 and maintained stable for 50 h almost without deactivation. The formation of Ce 1−x Ni x O 2−y solid solution uniformly disperses numerous Ni species in the CeO 2 lattice, effectively inhibiting Ni aggregation. This highly dispersed Ni weakens CO adsorption and facilitates its direct desorption without excessive hydrogenation. Moreover, the catalyst remains well-dispersed state even after reduction. The formed Ce 1−x Ni x O 2−y solid solution generates abundant oxygen vacancies on the catalyst surface, enhancing H 2 dissociation. The catalyst’s pore size distribution is also modified, creating stacked pores that favor reactant diffusion and expose more active centers. In-situ DRIFTS experiments demonstrate that Ce-OH plays a pivotal role in CO 2 adsorption on the 5Ni/CeO 2 -A catalyst, while the stabilization of bicarbonate and formate intermediates by the highly dispersed Ni further promotes catalytic performance. This study introduces a novel preparation method and provides valuable insights for designing Ni-based catalysts with exceptional CO selectivity.
研究领域:
催化化学
·
材料科学
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2024
·
IF 20.2
Mengyuan Zhang,Xiaoyan Lu,Kongliang Luo,Jian Ye,Jia li Dong,Nana Lu,Xiaopeng Wang,Qiang Niu,Pengfei Zhang,Sheng Dai
Ubiquitous presence of SO 2 usually shows adverse effects on industrial catalysis. Herein, a concept of engineering entropy to design SO 2 resistance oxide catalysts is proposed. (Ni 0.2 Mg 0.2 Cu 0.2 Zn 0.2 Co 0.2 )Fe 2 O 4 showed excellent performance (the CO 2 conv. = 41.4%, CO selec. = 99.6% at 400°C) compared to the control samples in the reverse water–gas shift (RWGS). In addition, (Ni 0.2 Mg 0.2 Cu 0.2 Zn 0.2 Co 0.2 )Fe 2 O 4 had the SO 2 -tolerant ability (the CO 2 conv. = 38.5%, CO selec. = 99.2% at 400°C) after being poisoned with 1000 ppm SO 2 at 400°C for 1 h. In sharp contrast, the control samples NiFe 2 O 4, MgFe 2 O 4, CuFe 2 O 4 and CoFe 2 O 4 lost their activity. O 1S XPS indicated that (Ni 0.2 Mg 0.2 Cu 0.2 Zn 0.2 Co 0.2 )Fe 2 O 4 had higher oxygen vacancy concentrations. SO 2 resistance mechanism was studied by infrared spectroscopy, SO 2 -TPD, in situ S 2p XPS and the DFT results, confirming that the low SO 2 adsorption energy of (Ni 0.2 Mg 0.2 Cu 0.2 Zn 0.2 Co 0.2 )Fe 2 O 4 , which was attributed to the lower Gibbs free energy. This work may inspire the rational design of SO 2 -resistant catalysts.
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高影响因子
JOURNAL OF THE ENERGY INSTITUTE
·
2026
·
IF 6.5
Zhi-Xin Li,Hui-Jie Cheng,Yi-Han Zhang,Cong-Jian Pan,Wei-Wei Yan,Wen-Long Mo,Xiao-Qin Yang,Cai-Xia Ju,Xiao-Yu Zhang,Zhi-Hao Ma,Xian-Yong Wei,Sheng Li
Crystallinity engineering of oxide supports has emerged as a powerful strategy to enhance the performance of supported catalysts, yet its application in complex oxides like lanthanum oxycarbonate (La 2 O 2 CO 3 ) remains underexplored. Here, we demonstrated that precise control of La 2 O 2 CO 3 crystallinity via calcination temperature tuning significantly improved the reverse water-gas shift (RWGS) reaction performance of Cu-based catalysts. CuLa500 catalyst, prepared at 500 °C, exhibited superior activity and stability compared to its high-crystallinity counterpart (CuLa800, 800 °C), achieving a CO 2 conversion of 54.4% and near-unity CO selectivity (>99.9%) at 600 °C under high space velocity conditions. Systematic characterization revealed that reduced crystallinity strengthens Cu-support interactions, optimizing CO 2 adsorption while enhancing structural robustness. This work not only establishes a scalable method for RWGS catalyst optimization but also provides mechanistic insights into the role of crystallinity in complex oxide-supported systems, offering a blueprint for advancing multiphase catalysis in energy-related reactions.
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DOI
高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Shiyan Li,Xu Liu,Jun Ma,Feifei Xu,Yuan Lyu,Siglinda Perathoner,Gabriele Centi,Yuefeng Liu
The high-temperature reverse water–gas shift (RWGS) is an industrially relevant reaction. Cu-based catalysts easily sinter and deactivate under these conditions. We demonstrate that it is possible to obtain high-performance and stable catalysts by modifying the mechanism of action. Cu/CeOx-MgO (denoted as Cu/CexMgy) catalysts were developed in which Cu nanoparticles mostly generate spillover H that migrates to support sites where CO2 is selectively reduced, with the rate controlled by the oxide–oxide CeOx-MgO interface. An optimal Cu/Ce0.05Mg0.95 catalyst (in terms of performance at the lowest possible Ce amount) exhibits a near-equilibrium CO2 conversion with a reaction rate of 516.0 μmol·gcat–1·s–1, near-total selectivity to CO at 600 °C, and a high space-velocity of 300,000 mL·gcat–1·h–1. These are among the top performances in the RWGS reaction. Extensive characterization data have proven that the surface-abundant Ce-[Ov]-Mg sites play a critical role in CO2 adsorption/activation as well as the carrier for the spillover of hydrogen species. The mechanism is substantially different from those indicated for Cu-based catalysts for CO2 hydrogenation. By decoupling H and CO2 activation sites and realizing efficient surface mobility of H-spillover species via an enhanced oxide–oxide interface, it is possible to maintain the overall stability and activity of the catalyst when the Cu nanoparticles sinter at a high temperature (i.e., ≥600 °C).
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DOI
高影响因子
Molecular Catalysis
·
2026
·
IF 4.3
Peng Zhang,Guang-Hui Liu,Yao-Shun Wen,Yu-Hong Kang,Yang-Fan Yin,Sheng Li,Zhi-Hao Ma,Zhi-Xin Li
Crystallinity engineering of La 2 O 2 CO 3 boosts RWGS reaction performance. • Cu/La-24 achieves 58.3% CO 2 conversion with 99.9% CO selectivity at 600 °C. • Higher crystallinity strengthens Cu-support interaction and inhibits catalyst sintering. Reverse water-gas shift (RWGS) reaction offers a promising route for CO production and CO 2 utilization, but its industrialization has been hindered due to the lack of efficient catalysts. Among non-precious alternatives, Cu-based catalysts show high CO selectivity but suffer from poor thermal stability and rapid deactivation. Here, La 2 O 2 CO 3 support crystallinity engineering was adopted to enhance the performance over Cu-based catalysts. Cu/La-24 (high support crystallinity) and Cu/La-6 (low support crystallinity) catalysts were synthesized and evaluated. Compared with Cu/La-6 catalyst, Cu/La-24 catalyst exhibited a better CO 2 conversion (58.3% at 600 °C), while improving the reaction rate and catalytic stability. Characterization results revealed that higher crystallinity strengthened metal-support interaction, enhanced CO 2 adsorption capacity and inhibited catalysts sintering, collectively boosting catalytic performance. This work demonstrates that crystallinity regulation is an effective strategy for designing stable and active Cu-based catalysts, paving the way for designing more efficient catalysts for RWGS reaction. Download: Download high-res image (182KB) Download: Download full-size image
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高影响因子
Nature Communications
·
2026
·
IF 18.1
Ye Daoping,Wu Zihe,Feng Yifan,Lei Jiwei,Niu Jin,Wu Hao,Cheng Chong,Tang Shengwei,Li Shuang
Among CO 2 emission mitigation strategies, the reverse water-gas shift (RWGS) reaction represents a promising route for selective CO 2 -to-CO conversion, enabling subsequent valorization. However, designing selective and stable non-noble metal catalysts for RWGS remains a persistent challenge. In this study, we report a Ni site-induced localized accelerated carbonization process to produce noble metal-like active Ni-WC nano-islands for high-performance RWGS catalysis. Benefiting from the unique structures, the Ni 0.02 WC/WO 2 -NIs catalyst exhibits exceptionally high RWGS activities, with a CO production rate of 2340 mol CO ·mol WC -1 ·h -1 and over 97% CO selectivity. Even after 100 hours of continuous testing at 500 °C, the activity loss of Ni 0.02 WC/WO 2 -NIs was only 0.5%. Unlike the conventional catalyst structure in the RWGS reaction, we demonstrate that the nano-island WC structure with stretch strain ensures the space limitation of electron-rich Ni sites for CO desorption and H 2 dissociation. Integrated in-situ DRIFTS, Raman spectroscopy, and DFT calculations reveal that dual-functional WC/WO x interfaces enhance catalyst activity through bidentate carbonate formation and intensified hydrogen spillover. We suggest that the design of new, efficient, and selective Ni-based noble-metal-like catalysts with nano-island structure through interface synergistic effects offers a promising path to engineering superior RWGS catalysts for CO 2 reduction.
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DOI
PubMed
高影响因子
JOURNAL OF THE ENERGY INSTITUTE
·
2025
·
IF 6.2
Peng Zhang,Guang-Hui Liu,Yao-Shun Wen,Yu-Hong Kang,Yang-Fan Yin,Sheng Li,Zhi-Xin Li,Zhi-Hao Ma
Morphology engineering plays a pivotal role in boosting catalytic performance over heterogeneous catalysis. However, although Y 2 O 3 (a rare earth oxide) has been found to possess various morphologies, including nanoplate (NP), nanosphere (NS) and nanorod (NR), the lack of understanding of its catalytic mechanism still limits its further application. Herein, catalytic mechanism of Y 2 O 3 morphologies in reverse water-gas shift (RWGS) reaction over Cu-based catalysts was systematically investigated. Although Y 2 O 3 morphologies don’t affect CO selectivity, it has a significant impact on CO 2 conversion and stability. Systematic characterization reveals that Y 2 O 3 morphologies not only can optimize the CO 2 adsorption capacity and Cu nanoparticles size to enhance catalytic activity, but also can regulate the metal-support interaction to improve catalytic stability. The order of activity and stability of the Cu/Y 2 O 3 catalysts from high to low is: Cu/ NP Y 2 O 3 > Cu/ NR Y 2 O 3 > Cu/ NS Y 2 O 3 . This work clarifies the morphological-performance relationship in rare earth oxide-Y 2 O 3 , providing a new approach for the design of high-performance Cu-based catalysts for RWGS reaction and promoting the application of morphology engineering in heterogeneous catalysis.
研究领域:
多相催化
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材料化学
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纳米材料
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能量转换
·
催化反应工程
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DOI
高影响因子
APPLIED CATALYSIS B-ENVIRONMENTAL
·
2026
·
IF 19.7
Wanyin Xu,Yuanhao Chen,Tianhe Gao,Zihan Wang,Wenkang Miao,Peng Wang,Qianqian Li
Successfully tailored a dual-site architecture comprising Cu + /Ni δ+ -O V -Ti and CuNi NPs on the ultra-small TiO 2 support-derived from MIL-125(Ti). • Deeply revealed the defect rich Cu + /Ni δ+ -O V -Ti site promotes CO 2 adsorption, while the CuNi NPs with electron redistribution facilitates H 2 adsorption and desorption of the product CO. • Significantly enhanced the RWGS reaction activity and sintering-resistance. Copper (Cu)-based catalysts hold promise for the reverse water-gas shift (RWGS) reaction because of their 100% selectivity toward CO. However, their low intrinsic activity, and deactivation caused by irreversible sintering during RWGS reaction remain persistent challenges. Herein, we report a pore adsorption strategy to simultaneously achieve electronic structure modulation and preserve microstructure stability during the RWGS reaction. Specifically, a MOF-derived TiO 2 -supported CuNi catalyst is constructed with dual active sites consisting of Cu + /Ni δ+ -O V -Ti sites and CuNi nanoparticles (NPs). The optimized catalytic performance achieves CO 2 conversion of 37.1% with CO selectivity of 99.9% and operates stably for 200 h at 450 ℃, placing its performance among the advanced Cu-based catalysts reported to date. Atomic/electronic structure characterization and density functional theory calculations demonstrate that Cu + /Ni δ+ -O V -Ti sites with enhanced charge redistribution capability promote CO 2 adsorption. The CuNi NP sites with electronic interaction enhance H 2 adsorption and moderate CO adsorption. This work provides a rational design strategy for highly active, selective and stable Cu-based RWGS catalysts. Download: Download high-res image (286KB) Download: Download full-size image Dual active sites consisting of Cu + /Ni δ+ -O V -Ti sites and CuNi NPs are constructed in the MOF-derived CuNi/TiO 2 catalyst, enabling electronic modulation and structural stabilization for enhanced RWGS reaction.
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DOI
高影响因子
CHEMICAL ENGINEERING JOURNAL
·
2023
·
IF 15.1
Zequn Zhang,Yuan Shu,Qian Liu,Shuxian Bi,Pengfei Zhang
Colloidal nanoparticles with uniform particle size distribution, tailored exposed facets, and controllable compositions appealed to broad interests in heterogeneous catalysis. Nevertheless, due to the strong attachment of capping agents to the nanoparticles, cleaning the nanoparticle surface without changing the size of nanoparticles remains a significant challenge. Herein, based on the double confinement of the strong metal-support interaction (SMSI) effect and carbon encapsulation, the well-stabilized Ni-ZnO-S3 catalyst was successfully synthesized. The size of Ni nanoparticles after calcination in the sequence of H 2 -N 2 mixture, air, and H 2 -N 2 mixture remained below 5 nm. Due to no significant size change in Ni nanoparticles, the prepared Ni-ZnO-S3 catalyst served well as model catalysts in the RWGS reaction, where the CO 2 conversion and CO yield increased proportionally to the Ni loading weight. According to the result of in-situ FTIR, an associative mechanism of RWGS reaction over Ni-ZnO-S3 was also identified. Therefore, this dual protect strategy provides a potential solution for building highly anti-sintering catalysts based on the colloidal synthesis route.
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高影响因子
Sustainable Energy & Fuels
·
2020
·Vol. 4
·期 6
·2937-2949
·
IF 5.503
Xin Hu,Xiaosong Hu,Qingxin Guan,Wei Li
Converting CO2 to CO via the reverse water gas shift (RWGS) reaction is an important route to reducing greenhouse gas emissions, and catalysts using copper and zinc as active components have been extensively studied for this reaction. Herein, the coordination and acid etching of trimesic acid (H3BTC) were used to assemble and regulate the Cu and ZnO components in the catalyst. First, Cu-HKUST-1 was synthesized by the self-assembly of H3BTC and copper ions, which limited the sintering and agglomeration of Cu nanoparticles in the subsequent carbonization and self-reduction process. Second, ZnO particles were etched by H3BTC to form the complex of H3BTC with Zn and to redisperse Zn species. Under the dual action of H3BTC, carbon-coated bimetal nanoparticles with a size of 2–6 nm were obtained on the fumed silica after pyrolysis at high temperature. The prepared Cu@C–ZnO/SiO2 catalyst can achieve 31.4% CO2 conversion and 99% CO selectivity in RWGS reaction in a fixed bed reactor at 400 °C and 3 MPa. Besides, we also found that the molar ratio of Cu/Zn, metal components, and the introduction order of H3BTC all affected the structure and composition of the catalyst, thus affecting the catalytic activity. This study provides an excellent strategy for the design and synthesis of catalysts containing copper and zinc components.
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高影响因子
ACS Catalysis
·
2025
·
IF 13.1
Shuo Cao,Ying Ma,Wei Chu,Bingsen Zhang,Bo Peng,Yuefeng Liu
Molybdenum carbides have received attention for the reverse water gas shift (RWGS) reaction. Normally, MoCx-based catalysts are synthesized via a high-temperature carbonization of 1100 K, leading to the agglomeration of the active phase. In order to minimize the atomic motion leading to single growth, insertion of heteroatoms has been attempted with the usage of components in the catalyst substrate. The current work applied the self-assembling strategy to prepare a Mo–O–Al composite instead of traditional impregnation before carburization. The dynamic structure evolution and detailed coordination environment of the active phase are investigated by in situ X-ray diffraction, quasi in situ X-ray photoelectron spectroscopy, in situ transmission electron microscopy, and temperature-programmed surface reaction techniques. Our findings reveal that Al doping enables carburization at a lower temperature (200 °C) via the topotactic pathway, yielding α-MoCx (fcc); even at a loading as high as 40 wt %, the catalyst maintains an ultrasmall particle size (1 nm). The optimized catalyst exhibits a RWGS reaction rate of 52.1 μmolCO2·gMo–1·s–1 at 400 °C, representing a 2.5-fold enhancement over bulk β-Mo2C. This work provides a possible solution for maintaining high dispersion at high metal loading for catalyst preparation, specially requiring a high temperature during either synthesis or reaction.
研究领域:
催化
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材料科学
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化学合成
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表面化学
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纳米技术
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DOI
高影响因子
JOURNAL OF THE ENERGY INSTITUTE
·
2024
·
IF 5.6
Zheng Bo,Mengyu Cao,Yaolin Wang,Jianhua Yan,Kefa Cen,Xin Tu
Plasma catalytic CO 2 hydrogenation has emerged as a promising approach for converting CO 2 into valuable chemicals such as CO, offering a potential solution to mitigate greenhouse gas emissions. In this study, we investigate the synergistic effect between plasma and a Cu/Ti 3 C 2 T x MXene catalyst for CO 2 hydrogenation via the reverse water gas shift (RWGS) reaction in a dielectric barrier discharge (DBD) reactor. Our findings reveal a significant enhancement in CO 2 conversion (33.1%) and CO yield (31.9%) when using the Cu/Ti 3 C 2 T x catalyst compared to plasma alone or with a Ti 3 C 2 T x foam. Plasma treatment creates unsaturated Ti sites on the Ti 3 C 2 T x surface, dramatically improving CO 2 adsorption and activation, while Cu nanoparticles significantly enhances the activation and dissociation of H 2 molecules on the catalyst surface. These surface adsorbed hydrogen species readily hydrogenate adsorbed CO 2 molecules through the Langmuir-Hinshelwood mechanism. Furthermore, these surface hydrogen species can also participate in the conversion of gas-phase CO 2 molecules through the Eley-Rideal pathway. This work sheds light on the synergistic plasma catalytic mechanism and provide insights for optimizing CO 2 hydrogenation processes using MXene catalysts.
研究领域:
化学工程
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催化
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环境科学
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等离子体化学
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高影响因子
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