物相到性能: 碳化钼在逆水煤气变换反应中的先进作用

doi:10.1016/S1872-2067(26)65036-X

催化学报 ›› 2026, Vol. 85: 1-12.DOI: 10.1016/S1872-2067(26)65036-X

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物相到性能: 碳化钼在逆水煤气变换反应中的先进作用

Fleur A. E. Bruekers, Tess I. van Benthem, Rajamohanan Sobhana Anju(), N. Raveendran Shiju()

阿姆斯特丹大学范特霍夫分子科学研究所催化工程组, 阿姆斯特丹, 荷兰

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),
n.r.shiju@uva.nl (N. R. Shiju).
作者简介:
¹共同第一作者.

Phase to performance: The advancing role of molybdenum carbides in reverse water-gas shift reaction

Fleur A. E. Bruekers, Tess I. van Benthem, Rajamohanan Sobhana Anju(), N. Raveendran Shiju()

Catalysis Engineering Group, Van ‘t Hoff Institute for Molecular Sciences, University of Amsterdam, Science Park 904, 1090GD Amsterdam, The Netherlands

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),
n.r.shiju@uva.nl (N. R. Shiju).
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.
Shiju Raveendran leads the Catalysis Engineering Group at the University of Amsterdam. He earned his Ph.D. in catalysis from the National Chemical Laboratory in Pune, India, and was subsequently awarded a prestigious Royal Society (UK) Postdoctoral Fellowship. He carried out postdoctoral research in both the United Kingdom and the United States before joining the University of Amsterdam as a faculty member. He currently serves as Editor-in-Chief of the Elsevier journal Sustainable Chemistry for Climate Action and is a member of the editorial boards of FlatChem and EnergyChem. His honors include the Amsterdam Science Park Ideas Prize and the J. N. Mukherjee Memorial Award from the Indian Chemical Society, recognizing his societally impactful contributions to Chemical Engineering and Green Chemistry. His research centres on the development of sustainable technologies by integrating reaction engineering, chemistry, and materials science.
¹Contributed equally to this work.

摘要/Abstract

摘要：

碳化钼(MoC_x)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, MoC_x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、MoC_x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MoC_x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.

关键词: 碳化钼, ·逆水煤气变换反应, CO₂利用, 催化, CO₂加氢

Abstract:

Molybdenum carbides (MoC_x) are rapidly emerging as efficient catalysts for the reverse water-gas shift (RWGS) reaction, outperforming conventional transition metals with their unique blend of noble-metal-like reactivity, exceptional thermal stability, and scalability. Recent advances in 2024-2025 have unlocked the excellent potential of the previously underexplored α-MoC phase, revealing unprecedented activity, robust CO selectivity, and dynamic carbidic carbon participation in CO₂ activation. These advances, alongside in situ mechanistic insights and phase-activity correlations, make a compelling case for MoC_x as a transformative platform for RWGS and downstream CO₂ valorization. Despite these advances, critical questions remain regarding the precise role of surface carbon vacancies, the long-term stability of MoC_x under dynamic RWGS conditions, the scalability of synthesis methods, and the durability for industrial deployment. This perspective provides the first focused synthesis of recent developments, while outlining current challenges and future research opportunities needed to position MoC_x catalysts at the forefront of circular carbon technologies and industrial CO₂ utilization.

Key words: Molybdenum carbide, Reverse water-gas shift, CO₂ utilization, Catalysis, CO₂ hydrogenation

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.

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图/表 5

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 g_cat^-1 h^-1)	CO rate (mmol g_cat^-1 h^-1)	Temperature (°C)	Ref.
2D-Mo₂C (2021)	(hexagonal)	120000	142.3	430	[18]
β-Mo₂C (2017)	β-Mo₂C (HCP)	300000	720.0	600	[14]
Nanowired β-Mo₂C (2016)	β-Mo₂C (HCP)	36000	61.7	600	[10]
Nanowired α-MoC_1-_x (2016)	cubic α-MoC_1-_x (FCC)	36000	61.7	600	[10]
cubic α-Mo₂C (2024)	α-Mo₂C (FCC)	100000	395.0	600	[13]
α-Mo₂C (2017)	hexagonal α-Mo₂C (hexagonal)	3000	1.7	400	[8]
Co/β-Mo₂C (7.5 wt%) (2014)	β-Mo₂C (HCP)	300000	49.8	300	[15]
Cu/β-Mo₂C (1.3 wt%) (2017)	β-Mo₂C (HCP)	300000	1703.0	600	[14]
Cs-Mo₂C (2019)	β-Mo₂C (HCP)	12000	24.6	600	[16]
1K-Cu/Mo₂C (2021)	β-Mo₂C	84000	176.0	600	[32]
K-Mo₂C@γ-Al₂O₃ (1:4:15) (20 wt%) (2022)	β-Mo₂C	3600	71.2	300	[33]
Mo_xC/SiO₂ (2022)	β-Mo₂C (HCP) & MoC (FCC)	20000	17.0	400	[19]
Mo_xC/Al₂O₃ (2022)	—	20000	14.8	400	[19]
MoC (2024)	hexagonal β-Mo₂C → hexagonal MoC	2840000	7544.6	600	[5]
α-MoC (2025)	α-MoC (FCC)	1800000	926,6	300	[11]
3D printed Mo₂C (10 wt% Mo) (2024)	δ-cubic MoC : η-Mo₃C₂	1187	17.6	600	[34]
Mo_n-Mo₂C cluster (1.3 wt% Mo) (2024)	β-Mo₂C	30000	2,071	400	[35]
Ir-MoO₃ (0.5 wt% Ir) (2024)	cubic α-MoC (FCC)	2000000	17500	600	[36]

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.

Table 2 RWGS pathways over representative Mo-C catalysts.

Catalyst	Dominant RWGS pathway	Remarks
β-Mo₂C (bulk/nanocrystalline) [18]	dissociative	Mo-terminated Mo₂C surfaces favor CO₂ dissociation.
α-Mo₂C (bulk/nanocrystalline) [13]	H₂-assisted redox mechanism	phase purity, weak CO binding, and interstitial O underpin performance
α-MoC (FCC) [11]	carbon cycle	dynamic carbon flux; Bulk-surface-gas exchange of carbon; lattice carbon participation than pure surface dissociation.
α-MoC with MoO_xC_y [36]	carbon cycle (Vacancy mediated)	distinct from classic redox/associative mechanism; CO₂-derived C inserts into Mo-Mo vacancies on MoO_xC_y, forms CO, and the vacancy regenerates by abstracting carbidic C.
In-situ carburized H_xMoO_y→MoC [5]	activation-driven	CO induced in situ carburization under RWGS; very high CO productivity rate
α-MoC_1-_x [10]	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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物相到性能: 碳化钼在逆水煤气变换反应中的先进作用

Phase to performance: The advancing role of molybdenum carbides in reverse water-gas shift reaction

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