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).
研究领域:
化学工程
·
催化材料
✓ 已验证
产品关联
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.
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
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.
研究领域:
催化化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
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
✓ 已验证
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.
研究领域:
催化化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2023
·Vol. 33
·期 16
·2214215
·
IF 19
Xiaosong Hu,Xinyu Liu,Xin Hu,Chaoyue Zhao,Qingxin Guan,Wei Li
Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO 2 hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnN x @C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N 4 sites and low valence CuN x clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N 4 and N 4 structures, which show strong Lewis basicity and has strong adsorption for *CO 2 and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO 2 conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO 2 conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO 2 . In the catalytic process, CuN x not only adsorbs and activates H 2 , but also cooperates with the adjacent Zn-N 4 and N 4 structures to jointly activate CO 2 molecules and further promotes the hydrogenation of CO 2 . This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.
研究领域:
化学
·
催化材料科学
✓ 已验证
产品关联
DOI
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.
✓ 已验证
DOI
高影响因子
ACS Catalysis
·
2024
·
IF 11.3
Shuo Cao,Zun Guan,Ying Ma,Bing Xu,Jun Ma,Wei Chu,Riguang Zhang,Giuliano Giambastiani,Yuefeng Liu
The design and synthesis of highly efficient and selective catalysts for CO2 thermal reduction remain a challenging issue of modern catalysis. Molybdenum carbide has attracted great interest in CO2-to-CO conversion (Reverse Water Gas Shift process, RWGS) because of its ability to dissociate CO2 and H2. However, single dominant Mo- or C-terminated facets of molybdenum carbide are unlikely to activate CO2 and H2 molecules simultaneously. Herein, we demonstrate how structural diversity of cogenerated molybdenum species (i.e., Mon nanoclusters and Mo2C nanoparticles) on the surface of an oxygen-enriched C-carrier boosts synergistically the chemoselective RWGS process with rates up to 581 μmolCO2·gMo–1·s–1 with CO selectivity > 99% already at 400 °C under an H2-rich environment. This catalytic outcome ranks among the highest reported so far for molybdenum carbide- or noble metal-based catalysts in the process, and it is up to 1.8 times higher than that measured on Mo2C-based nanoparticles. The enhanced reactivity of the structurally mixed catalyst has been ascribed to a synergistic modulation of the geometrical and electronic structure of different Mo sites that reduces the temperature at which CO production starts and facilitates the chemoselective CO desorption pathway. Experimental and in silico studies have also unveiled the existence of a linear correlation between the percentage of high-valence molybdenum species in the metal active-phase composition (Moδ+ %) and the increase in the RWGS rate.
研究领域:
催化化学
·
材料科学
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
Journal of CO2 Utilization
·
2021
·
IF 7.132
Bowen Lu,Yongqing Xu,Zewu Zhang,Fan Wu,Xiaoshan Li,Cong Luo,Liqi Zhang
Cu-based catalysts had been widely used in CO 2 hydrogenation process for their excellent performance and high selectivity. Micron-sized Cu powder obtained by ball milling exhibited poor CO 2 activity for its large particle size and small specific surface area, limited its catalytic application. In this work, micron Cu powder was modified with CeO 2 species synthesized from different cerium precursor salts via a solution auto-combustion method to investigate CO 2 hydrogenation activity. This work revealed that CeO 2 species formed from cerium acetate precursor salt achieved excellent CO 2 performance (1.64 mol/g cat .h at 400 °C), which was 3.8 times and 6000 times higher than that from cerium nitrate salt or cerium chloride salt, respectively. Interestingly, a thick dense CeO 2 shell would be formed on micron Cu generated from cerium(III) chloride precursor salt, which inhibited CuO x reduction and had the opposite effect for RWGS reaction. In addition, the CuO x species in CeO 2 @Cu synthesized from cerium chloride salt resulted in the CH 4 selectivity. The enhancement performance of the CeO 2 @Cu prepared from cerium acetate salt and cerium nitrate salt could be attributed to the oxygen defects formed around the Cu-Ox-Ce interface area and metallic Cu in the RWGS reaction. Cerium precursor salts enhanced the structural integrity of CeO 2 @Cu and played a vital role in RWGS reaction. These results will support a new direction for exploring micron Cu powder in Cu-based catalysts for CO 2 utilization.
研究领域:
化学工程
·
材料科学
·
催化反应
✓ 已验证
产品关联
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
✓ 已验证
产品关联
DOI
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.
✓ 已验证
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
·
材料化学
·
纳米材料
·
能量转换
·
催化反应工程
✓ 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）