The water–gas shift (WGS) reaction is an industrially important source of pure hydrogen (H2) at the expense of carbon monoxide and water1,2. This reaction is of interest for fuel-cell applications, but requires WGS catalysts that are durable and highly active at low temperatures3. Here we demonstrate that the structure (Pt1–Ptn)/α-MoC, where isolated platinum atoms (Pt1) and subnanometre platinum clusters (Ptn) are stabilized on α-molybdenum carbide (α-MoC), catalyses the WGS reaction even at 313 kelvin, with a hydrogen-production pathway involving direct carbon monoxide dissociation identified. We find that it is critical to crowd the α-MoC surface with Pt1 and Ptn species, which prevents oxidation of the support that would cause catalyst deactivation, as seen with gold/α-MoC (ref. 4), and gives our system high stability and a high metal-normalized turnover number of 4,300,000 moles of hydrogen per mole of platinum. We anticipate that the strategy demonstrated here will be pivotal for the design of highly active and stable catalysts for effective activation of important molecules such as water and carbon monoxide for energy production.
Subscribe to Journal
Get full journal access for 1 year
only $3.90 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Tax calculation will be finalised during checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
The main data supporting the findings of this study are available within the paper and its Supplementary Information. Additional data are available from the corresponding authors upon reasonable request.
Zhai, Y. et al. Alkali-stabilized Pt-OHx species catalyze low-temperature water–gas shift reactions. Science 329, 1633–1636 (2010).
Rodriguez, J. A. et al. Activity of CeOx and TiOx nanoparticles grown on Au(111) in the water–gas shift reaction. Science 318, 1757–1760 (2007).
Ladebeck, J. R. & Wagner, J. P. in Handbook of Fuel Cells (eds Vielstich, W., Lamm, A. & Gasteiger, H. A.) Ch. 16, 197 (Wiley, 2003).
Yao, S. et al. Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water–gas shift reaction. Science 357, 389–393 (2017).
Yang, M. et al. A common single-site Pt(ii)–O(OH)x– species stabilized by sodium on “active” and “inert” supports catalyzes the water–gas shift reaction. J. Am. Chem. Soc. 137, 3470–3473 (2015).
Fu, Q., Saltsburg, H. & Flytzani-Stephanopoulos, M. Active nonmetallic Au and Pt species on ceria-based water–gas shift catalysts. Science 301, 935–938 (2003).
Yang, M. et al. Catalytically active Au–O(OH)x– species stabilized by alkali ions on zeolites and mesoporous oxides. Science 346, 1498–1501 (2014).
Zugic, B. et al. Probing the low-temperature water–gas shift activity of alkali-promoted platinum catalysts stabilized on carbon supports. J. Am. Chem. Soc. 136, 3238–3245 (2014).
Ding, K. et al. Identification of active sites in CO oxidation and water–gas shift over supported Pt catalysts. Science 350, 189–192 (2015).
Schweitzer, N. M. et al. High activity carbide supported catalysts for water gas shift. J. Am. Chem. Soc. 133, 2378–2381 (2011).
Li, Z. et al. Reactive metal–support interactions at moderate temperature in two-dimensional niobium-carbide-supported platinum catalysts. Nat. Catal. 1, 349–355 (2018).
Hunt, S. T. et al. Self-assembly of noble metal monolayers on transition metal carbide nanoparticle catalysts. Science 352, 974–978 (2016).
Lu, J., Aydin, C., Browning, N. D. & Gates, B. C. Hydrogen activation and metal hydride formation trigger cluster formation from supported iridium complexes. J. Am. Chem. Soc. 134, 5022–5025 (2012).
Fierro-Gonzalez, J. C. & Gates, B. C. Mononuclear AuIII and AuI complexes bonded to zeolite NaY: catalysts for CO oxidation at 298 K. J. Phys. Chem. B 108, 16999–17002 (2004).
Lu, J., Aydin, C., Browning, N. D. & Gates, B. C. Imaging isolated gold atom catalytic sites in zeolite NaY. Angew. Chem. Int. Ed. 51, 5842–5846 (2012).
Miller, J. T. et al. The effect of gold particle size on Au–Au bond length and reactivity toward oxygen in supported catalysts. J. Catal. 240, 222–234 (2006).
Dong, J. et al. Carbide-supported Au catalysts for water–gas shift reactions: a new territory for the strong metal–support interaction effect. J. Am. Chem. Soc. 140, 13808–13816 (2018).
Sabnis, K. D. et al. Water–gas shift catalysis over transition metals supported on molybdenum carbide. J. Catal. 331, 162–171 (2015).
Lin, L. et al. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts. Nature 544, 80–83 (2017).
Lin, J. et al. Remarkable performance of Ir1/FeOx single-atom catalyst in water gas shift reaction. J. Am. Chem. Soc. 135, 15314–15317 (2013).
Fu, Q., Deng, W., Saltsburg, H. & Flytzani-Stephanopoulos, M. Activity and stability of low-content gold-cerium oxide catalysts for the water–gas shift reaction. Appl. Catal. B 56, 57–68 (2005).
Murugappan, K. et al. Operando NAP-XPS unveils differences in MoO3 and Mo2C during hydrodeoxygenation. Nat. Catal. 1, 960–967 (2018).
Porosoff, M. D., Yang, X., Boscoboinik, J. A. & Chen, J. G. Molybdenum carbide as alternative catalysts to precious metals for highly selective reduction of CO2 to CO. Angew. Chem. Int. Ed. 53, 6705–6709 (2014).
Prosvirin, I. P., Bukhtiyarov, A. V., Bluhm, H. & Bukhtiyarov, V. I. Application of near ambient pressure gas-phase X-ray photoelectron spectroscopy to the investigation of catalytic properties of copper in methanol oxidation. Appl. Surf. Sci. 363, 303–309 (2016).
Mudiyanselage, K. et al. Importance of the metal-oxide interface in catalysis: in situ studies of the water–gas shift reaction by ambient-pressure X-ray photoelectron spectroscopy. Angew. Chem. Int. Ed. 52, 5101–5105 (2013).
Lin, L. et al. A highly CO-tolerant atomically dispersed Pt catalyst for chemoselective hydrogenation. Nat. Nanotechnol. 14, 354–361 (2019).
Namiki, T., Yamashita, S., Tominaga, H. & Nagai, M. Dissociation of CO and H2O during water–gas shift reaction on carburized Mo/Al2O3 catalyst. Appl. Catal. A 398, 155–160 (2011).
Kalamaras, C. M., Americanou, S. & Efstathiou, A. M. “Redox” vs “associative formate with –OH group regeneration” WGS reaction mechanism on Pt/CeO2: effect of platinum particle size. J. Catal. 279, 287–300 (2011).
Deng, W., Carpenter, C., Yi, N. & Flytzani-Stephanopoulos, M. Comparison of the activity of Au/CeO2 and Au/Fe2O3 catalysts for the CO oxidation and the water–gas shift reactions. Top. Catal. 44, 199–208 (2007).
Yang, M., Allard, L. F. & Flytzani-Stephanopoulos, M. Atomically dispersed Au– (OH)x species bound on titania catalyze the low-temperature water–gas shift reaction. J. Am. Chem. Soc. 135, 3768–3771 (2013).
de la Peña, F. et al. hyperspy/hyperspy: HyperSpy v1.5.2. https://doi.org/10.5281/zenodo.3396791 (2019).
Herzing, A. A. et al. Identification of active gold nanoclusters on iron oxide supports for CO oxidation. Science 321, 1331–1335 (2008).
Artiglia, L. et al. Introducing time resolution to detect Ce3+ catalytically active sites at the Pt/CeO2 interface through ambient pressure X-ray photoelectron spectroscopy. J. Phys. Chem. Lett. 8, 102–108 (2017).
Orlando, F. et al. The environmental photochemistry of oxide surfaces and the nature of frozen salt solutions: a new in situ XPS approach. Top. Catal. 59, 591–604 (2016).
This work received financial support from the Natural Science Foundation of China (21725301, 21932002, 21821004, 91645115, 51622211, 21577013, 21707015, 21872014, 21902018), the National Key R&D Program of China (2017YFB0602200, 2017YFA0700103, 2018YFA0305800), and the Beijing Outstanding Young Scientist Program (BJJWZYJH01201914430039). The X-ray absorption spectroscopy and X-ray diffraction experiments were conducted at the Shanghai Synchrotron Radiation Facility and the Beijing Synchrotron Radiation Facility. The Pt L3 edge X-ray absorption spectroscopy for 0.02 wt% Pt/α-MoC was conducted at beamline10-BM, MRCAT operations, Advanced Photon Source under contract number DEAC02-06CH11357. The AP-XPS experiments were conducted in Swiss Light Source synchrotron. D.M. acknowledges support from the Tencent Foundation through the XPLORER PRIZE.
The authors declare no competing interests.
Peer review information Nature thanks Matteo Cargnello and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Zhang, X., Zhang, M., Deng, Y. et al. A stable low-temperature H2-production catalyst by crowding Pt on α-MoC. Nature 589, 396–401 (2021). https://doi.org/10.1038/s41586-020-03130-6
Controlling phase transfer of molybdenum carbides by various metals for highly efficient hydrogen production
Journal of Energy Chemistry (2021)
Hydrogen generation from ammonia borane hydrolysis catalyzed by ruthenium nanoparticles supported on Co–Ni layered double oxides
Sustainable Energy & Fuels (2021)
ACS Nano (2021)
New Journal of Chemistry (2021)