Valorization of carbon dioxide into C1 product via reverse water gas shift reaction using oxide-supported molybdenum carbides

Andrew N. Kuhn; Rachel C. Park; Siying Yu; Di Gao; Cheng Zhang; Yuanhui Zhang; Hong Yang

doi:10.26599/CF.2024.9200011

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Research Article | Open Access

Valorization of carbon dioxide into C1 product via reverse water gas shift reaction using oxide-supported molybdenum carbides

Andrew N. Kuhn^{¹^,³}, Rachel C. Park^¹, Siying Yu^¹, Di Gao^¹, Cheng Zhang^¹, Yuanhui Zhang^², Hong Yang^¹

()

1Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, 600 South Mathews Avenue, Urbana, IL 61801, USA

2Department of Agricultural & Biological Engineering, University of Illinois at Urbana-Champaign, 1304 West Pennsylvania Avenue, Urbana, IL 61801, USA

3Present address: College of Engineering, Virginia Commonwealth University, 601 West Main Street, Richmond, VA 23284, USA

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Silica-supported nanometer-sized molybdenum carbide catalyst is applied to the valorization of carbon dioxide, achieving a high mass activity of 372 μmol_CO₂·g_Mo₂C ⁻¹∙s⁻¹ at 400 °C and 1109 μmol_CO₂·g_Mo₂C ⁻¹·s⁻¹ at 600 °C.

Abstract

Conversion of carbon dioxide (CO₂) to C1 products such as carbon monoxide (CO) is a critical step towards carbon valorization. The conversion has been largely carried out through the reverse water gas shift (RWGS) reaction using noble metal catalysts or copper-based nanostructures. Similarities in the electronic structures between beta phase molybdenum carbides (β-Mo₂C) and platinum-group metals make them promising alternatives to traditional catalysts. In this work, we studied the effect of oxide supports (MO_x, M = Al, Ce, Mg, Si, and Ti) on the formation and catalytic properties of β-Mo₂C nanoparticle catalysts. The β-Mo₂C/SiO₂ catalyst exhibited a mass activity of 372 μmol_CO₂∙ $g_{M o_{2} C}^{- 1}$ ∙s⁻¹ at 400 °C and 1109 μmol_CO₂∙ $g_{M o_{2} C}^{- 1}$ ∙s⁻¹ at 600 °C for the conversion of CO₂. The β-Mo₂C/SiO₂ catalysts also maintained selectivity and showed structural stability in the on-stream study. The enhanced catalytic performance could be attributed to the size of nanocatalysts (4.7 nm), whereas the stability is related to the interaction with SiO₂ and the low H₂:CO₂ feed ratio. This work highlights the application of amorphous silica in preparing metal carbide nanocatalysts. The rich defects and surface vacancies in the silica support greatly facilitate the high-rate and highly selective processes towards the valorization of CO₂.

Keywords

molybdenum carbide reverse water gas shift reaction carbon dioxide valorization

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References

[1]

Davis, S. J.; Caldeira, K.; Matthews, H. D. Future CO₂ emissions and climate change from existing energy infrastructure. Science 2010, 329, 1330–1333.

Catalyst type	Catalyst formula	FeedH₂:CO₂	SV(mL∙g⁻¹ ∙h⁻¹)	T(°C)	X_CO₂(%)	S_CO(%)	CO production(μmol_CO∙ $g_{M o_{2} C}^{- 1}$ ∙s⁻¹)	Ref.
Supported	25% β-Mo₂C/SiO₂	1	60,000	400	22	100	291	This work
	25% β-Mo₂C/SiO₂			600	40	100	535
	5% β-Mo₂C/SiO₂			400	6	100	372
	5% β-Mo₂C/SiO₂			600	17	100	1109
Bulk	β-Mo₂C_bulk			400	13	99	45
Bulk	β-Mo₂C_bulk			600	35	100	117
Supported	β-Mo₂C/Al₂O₃	3	24,000	400	21	99	184	43
	β-Mo₂C/Al₂O₃	3	24,000	600	42	100	368	43
	K-β-Mo₂C/Al₂O₃	3	3,000	300	18	96	189	46
	β-Mo₂C/C	4	60,000	400	12	100	40	40
	α-MoC/C	3	30,000	300	20	73	293	32
Bulk	β-Mo₂C	2	300,000	600	15	100	200	19
	β-Mo₂C	2	300,000	300	0.5	98	7	19
	β-Mo₂C	2	36,000	300	9	97	14	45
	α-Mo₂C	1	3,000	400	16	99	1	39
	β-Mo₂C	4	12,000	400	42	73	14	29
	β-Mo₂C	4	12,000	600	64	86	21	29