催化学报 ›› 2026, Vol. 85: 1-12.DOI: 10.1016/S1872-2067(26)65036-X
• 视角 • 下一篇
Fleur A. E. Bruekers, Tess I. van Benthem, Rajamohanan Sobhana Anju(
), N. Raveendran Shiju(
)
收稿日期:2025-09-22
接受日期:2025-12-12
出版日期:2026-06-18
发布日期:2026-05-18
通讯作者:
*电子信箱: a.rajamohanansobhana@uva.nl (R. S. Anju),作者简介:1共同第一作者.
Fleur A. E. Bruekers, Tess I. van Benthem, Rajamohanan Sobhana Anju(
), N. Raveendran Shiju(
)
Received:2025-09-22
Accepted:2025-12-12
Online:2026-06-18
Published:2026-05-18
Contact:
*E-mail: a.rajamohanansobhana@uva.nl (R. S. Anju),About author:Dr. Anju Rajamohanan Sobhana (University of Amsterdam), was a Marie Skłodowska-Curie Postdoctoral Fellow at the University of Amsterdam, The Netherlands (2024-2025). Dr. Anju serves as Assistant Professor at NSS College, Ottapalam, India since 2018. She received her Ph.D. degree from the Indian Institute of Technology (IIT) Madras (India) in 2015. She carried out postdoctoral research at Gulf University for Science and Technology (Kuwait), Texas A&M University at Qatar, and Qatar Energy Environment and Research Institute (Qatar). Her research interests mainly focus on organometallic chemistry, boron cluster chemistry, catalysis and CO2 valorisation. She has published 23 peer-reviewed research articles in leading international journals.1Contributed equally to this work.
摘要:
碳化钼(MoCx)具有独特的类贵金属反应活性、优异的热稳定性及规模化制备潜力, 其催化性能超越传统过渡金属, 成为逆水煤气变换(RWGS)反应的高效催化剂. 2024-2025年的最新研究进展显示, 此前未被充分探索的α-MoC相表现出巨大的应用潜力, 其具有高活性和高CO选择性, 且碳化物动态参与到二氧化碳活化过程中. 原位机理研究和物相-活性的构效关系等些研究进展表明, MoCx可用作RWGS和下游二氧化碳资源化利用的转换平台. 然而, 目前还存在一些关键问题有待解决, 如表面碳空位的确切作用、MoCx在动态RWGS条件下的长期稳定性、合成方法的规模化潜力, 以及在工业应用中的耐久性等. 本文集中综述了最近进展, 同时概述了将MoCx催化剂用于循环碳技术和工业二氧化碳利用所面临的当前挑战和未来研究方向.
Fleur A. E. Bruekers, Tess I. van Benthem, Rajamohanan Sobhana Anju, N. Raveendran Shiju. 物相到性能: 碳化钼在逆水煤气变换反应中的先进作用[J]. 催化学报, 2026, 85: 1-12.
Fleur A. E. Bruekers, Tess I. van Benthem, Rajamohanan Sobhana Anju, N. Raveendran Shiju. Phase to performance: The advancing role of molybdenum carbides in reverse water-gas shift reaction[J]. Chinese Journal of Catalysis, 2026, 85: 1-12.
| Catalyst (year of publication) | Phase (structure) | Space velocity (mL gcat-1 h-1) | CO rate (mmol gcat-1 h-1) | Temperature (°C) | Ref. |
|---|---|---|---|---|---|
| 2D-Mo2C (2021) | (hexagonal) | 120000 | 142.3 | 430 | [ |
| β-Mo2C (2017) | β-Mo2C (HCP) | 300000 | 720.0 | 600 | [ |
| Nanowired β-Mo2C (2016) | β-Mo2C (HCP) | 36000 | 61.7 | 600 | [ |
| Nanowired α-MoC1-x (2016) | cubic α-MoC1-x (FCC) | 36000 | 61.7 | 600 | [ |
| cubic α-Mo2C (2024) | α-Mo2C (FCC) | 100000 | 395.0 | 600 | [ |
| α-Mo2C (2017) | hexagonal α-Mo2C (hexagonal) | 3000 | 1.7 | 400 | [ |
| Co/β-Mo2C (7.5 wt%) (2014) | β-Mo2C (HCP) | 300000 | 49.8 | 300 | [ |
| Cu/β-Mo2C (1.3 wt%) (2017) | β-Mo2C (HCP) | 300000 | 1703.0 | 600 | [ |
| Cs-Mo2C (2019) | β-Mo2C (HCP) | 12000 | 24.6 | 600 | [ |
| 1K-Cu/Mo2C (2021) | β-Mo2C | 84000 | 176.0 | 600 | [ |
| K-Mo2C@γ-Al2O3 (1:4:15) (20 wt%) (2022) | β-Mo2C | 3600 | 71.2 | 300 | [ |
| MoxC/SiO2 (2022) | β-Mo2C (HCP) & MoC (FCC) | 20000 | 17.0 | 400 | [ |
| MoxC/Al2O3 (2022) | — | 20000 | 14.8 | 400 | [ |
| MoC (2024) | hexagonal β-Mo2C → hexagonal MoC | 2840000 | 7544.6 | 600 | [ |
| α-MoC (2025) | α-MoC (FCC) | 1800000 | 926,6 | 300 | [ |
| 3D printed Mo2C (10 wt% Mo) (2024) | δ-cubic MoC : η-Mo3C2 | 1187 | 17.6 | 600 | [ |
| Mon-Mo2C cluster (1.3 wt% Mo) (2024) | β-Mo2C | 30000 | 2,071 | 400 | [ |
| Ir-MoO3 (0.5 wt% Ir) (2024) | cubic α-MoC (FCC) | 2000000 | 17500 | 600 | [ |
Table 1 Summary of the molybdenum carbide catalysts including their crystal structure, catalytic performance (CO rate), and operational conditions (space velocity, temperature). All catalysts were reported at a pressure of 1 bar, except K-Mo2C@γ-Al2O3 reported at 20 bar.
| Catalyst (year of publication) | Phase (structure) | Space velocity (mL gcat-1 h-1) | CO rate (mmol gcat-1 h-1) | Temperature (°C) | Ref. |
|---|---|---|---|---|---|
| 2D-Mo2C (2021) | (hexagonal) | 120000 | 142.3 | 430 | [ |
| β-Mo2C (2017) | β-Mo2C (HCP) | 300000 | 720.0 | 600 | [ |
| Nanowired β-Mo2C (2016) | β-Mo2C (HCP) | 36000 | 61.7 | 600 | [ |
| Nanowired α-MoC1-x (2016) | cubic α-MoC1-x (FCC) | 36000 | 61.7 | 600 | [ |
| cubic α-Mo2C (2024) | α-Mo2C (FCC) | 100000 | 395.0 | 600 | [ |
| α-Mo2C (2017) | hexagonal α-Mo2C (hexagonal) | 3000 | 1.7 | 400 | [ |
| Co/β-Mo2C (7.5 wt%) (2014) | β-Mo2C (HCP) | 300000 | 49.8 | 300 | [ |
| Cu/β-Mo2C (1.3 wt%) (2017) | β-Mo2C (HCP) | 300000 | 1703.0 | 600 | [ |
| Cs-Mo2C (2019) | β-Mo2C (HCP) | 12000 | 24.6 | 600 | [ |
| 1K-Cu/Mo2C (2021) | β-Mo2C | 84000 | 176.0 | 600 | [ |
| K-Mo2C@γ-Al2O3 (1:4:15) (20 wt%) (2022) | β-Mo2C | 3600 | 71.2 | 300 | [ |
| MoxC/SiO2 (2022) | β-Mo2C (HCP) & MoC (FCC) | 20000 | 17.0 | 400 | [ |
| MoxC/Al2O3 (2022) | — | 20000 | 14.8 | 400 | [ |
| MoC (2024) | hexagonal β-Mo2C → hexagonal MoC | 2840000 | 7544.6 | 600 | [ |
| α-MoC (2025) | α-MoC (FCC) | 1800000 | 926,6 | 300 | [ |
| 3D printed Mo2C (10 wt% Mo) (2024) | δ-cubic MoC : η-Mo3C2 | 1187 | 17.6 | 600 | [ |
| Mon-Mo2C cluster (1.3 wt% Mo) (2024) | β-Mo2C | 30000 | 2,071 | 400 | [ |
| Ir-MoO3 (0.5 wt% Ir) (2024) | cubic α-MoC (FCC) | 2000000 | 17500 | 600 | [ |
Fig. 1. Crystal structures of HCP (A) and FCC (B) like catalysts (Mo: cyan; C: grey). Reprinted with permission from Ref. [17]. Copyright 2016, Elsevier Ltd. (C) Schematic depiction of cubic α-Mo2C (Mo: purple; C: grey). Reprinted with permission from Ref. [13], Copyright © 2024 The Author(s). (D) Schematic depiction of 2D-Mo2C (Mo: blue; C: grey). Reprinted with permission from Ref. [18]. Copyright 2021, The Author(s).
Fig. 2. (A) Carbidic-carbon-participation during the RWGS reaction over α-MoC catalysts. Reprinted with permission from Ref. 39. Copyright 2024, American Chemical Society should read as Reprinted with permission from Ref 35, Copyright © 2024 American Chemical Society. (B) HRETM images of MoC showing the structural evolution with carbon flow during RWGS reaction (top) and superimposition of successive images form the in situ HRTEM sequence (red for high temperature image, green for low temperature image and yellow is the overlap of red and green, bottom) Reprinted with permission from Ref. [11]. Copyright 2024, Wiley-VCH GmbH. (C) Schematic diagram of the positive feedback between catalytic activity and structural evolution of β-Mo2N under RWGS reaction. Reprinted with permission from Ref. [37]. Copyright 2024, The Author(s). (D) In-situ carburization of MoOx leading to the formation of β-Mo2C followed by hexagonal MoC. Reprinted with permission from Ref. [5]. Copyright 2024, Wiley-VCH GmbH. (E) Structural diversity of co-generated Mo species boosting RWGS activity. Reprinted with permission from Ref. [39]. Copyright 2024, American Chemical Society.
| Catalyst | Dominant RWGS pathway | Remarks |
|---|---|---|
| β-Mo2C (bulk/nanocrystalline) [ | dissociative | Mo-terminated Mo2C surfaces favor CO2 dissociation. |
| α-Mo2C (bulk/nanocrystalline) [ | H2-assisted redox mechanism | phase purity, weak CO binding, and interstitial O underpin performance |
| α-MoC (FCC) [ | carbon cycle | dynamic carbon flux; Bulk-surface-gas exchange of carbon; lattice carbon participation than pure surface dissociation. |
| α-MoC with MoOxCy [ | carbon cycle (Vacancy mediated) | distinct from classic redox/associative mechanism; CO2-derived C inserts into Mo-Mo vacancies on MoOxCy, forms CO, and the vacancy regenerates by abstracting carbidic C. |
| In-situ carburized HxMoOy→MoC [ | activation-driven | CO induced in situ carburization under RWGS; very high CO productivity rate |
| α-MoC1-x [ | associative | formate decomposition mechanism. |
Table 2 RWGS pathways over representative Mo-C catalysts.
| Catalyst | Dominant RWGS pathway | Remarks |
|---|---|---|
| β-Mo2C (bulk/nanocrystalline) [ | dissociative | Mo-terminated Mo2C surfaces favor CO2 dissociation. |
| α-Mo2C (bulk/nanocrystalline) [ | H2-assisted redox mechanism | phase purity, weak CO binding, and interstitial O underpin performance |
| α-MoC (FCC) [ | carbon cycle | dynamic carbon flux; Bulk-surface-gas exchange of carbon; lattice carbon participation than pure surface dissociation. |
| α-MoC with MoOxCy [ | carbon cycle (Vacancy mediated) | distinct from classic redox/associative mechanism; CO2-derived C inserts into Mo-Mo vacancies on MoOxCy, forms CO, and the vacancy regenerates by abstracting carbidic C. |
| In-situ carburized HxMoOy→MoC [ | activation-driven | CO induced in situ carburization under RWGS; very high CO productivity rate |
| α-MoC1-x [ | associative | formate decomposition mechanism. |
Fig. 3. (A) Comparison of CO productivity among molybdenum carbides (star symbol, 1-19) and other catalysts reported in literature (circle symbol, 20-36). (B) Comparison of CO selectivity (above the dashed line) of the different catalysts and the CO2 conversion (below the dashed line) over time on stream. Table S1 shows the performance metrics of the catalysts shown in Fig. 3 [8,10,11,13,15,16,18,19,32-35,43], along with additional state-of-the-art RWGS catalysts [16,44-58].
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