Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

Stottlemyer, Alan L.; Kelly, Thomas G.; Meng, Qingcai; Chen, Jingguang G.

doi:10.1016/j.surfrep.2012.07.001

Cited by 89 publications

(82 citation statements)

References 195 publications

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“…[12,13] The reactivity of WC has been partially attributed to the intercalation of C to the W lattice, which gives rise to a "Pt-like" d-band electronic density states (DOS). [14] Peppernick et al demonstrated that WC À ions exhibit isoelectronic correspondence with Pt À ions.[15] Because WC exhibits high thermal and electrochemical stability while resisting common catalyst poisons such as carbon monoxide and sulfur, [1][2][3] it has been identified as a suitable candidate to replace PGM catalysts in emerging renewable energy technologies, such as fuel cells and electrolyzers. [7][8][9][10][11][16][17][18] While there are many methods to synthesize WC nanoparticles (NPs), none of the current methods can simultaneously prevent sintering of the WC nanoparticles while also mitigating surface impurity deposition.…”

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confidence: 99%

“…Thus, despite the promising catalytic properties of model WC surfaces, the lack of synthesis methods to produce metal-terminated WC NPs of controlled sizes has prevented its wide-spread use as an earthabundant catalyst. [1,2,7,19] The high carburization temperatures (> ca. 700 8C) required to overcome the thermodynamic and kinetic barriers for carbon incorporation into the metal lattice induce uncontrollable particle sintering, generating particles with exceedingly low surface areas that are not suitable for commercial applications (Supporting Information , Figure S1).…”

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confidence: 99%

“…[1][2][3] Tungsten carbide (WC) has garnered much attention for its catalytic similarities to the platinum group metals [4] (PGMs) in several thermoand electrocatalytic reactions, such as biomass conversion, [2,5,6] hydrogen evolution and oxygen reduction, [7][8][9][10][11] and alcohol electrooxidation. [12,13] The reactivity of WC has been partially attributed to the intercalation of C to the W lattice, which gives rise to a "Pt-like" d-band electronic density states (DOS).…”

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Engineering Non‐sintered, Metal‐Terminated Tungsten Carbide Nanoparticles for Catalysis

2014

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Transition-metal carbides (TMCs) exhibit catalytic activities similar to platinum group metals (PGMs), yet TMCs are orders of magnitude more abundant and less expensive. However, current TMC synthesis methods lead to sintering, support degradation, and surface impurity deposition, ultimately precluding their wide-scale use as catalysts. A method is presented for the production of metal-terminated TMC nanoparticles in the 1-4 nm range with tunable size, composition, and crystal phase. Carbon-supported tungsten carbide (WC) and molybdenum tungsten carbide (Mo x W 1Àx C) nanoparticles are highly active and stable electrocatalysts. Specifically, activities and capacitances about 100-fold higher than commercial WC and within an order of magnitude of platinumbased catalysts are achieved for the hydrogen evolution and methanol electrooxidation reactions. This method opens an attractive avenue to replace PGMs in high energy density applications such as fuel cells and electrolyzers.Early transition-metal carbides (TMCs) are earth-abundant materials with established commercial use in a variety of applications owing to their favorable optical, electronic, mechanical, and chemical properties. [1][2][3] Tungsten carbide (WC) has garnered much attention for its catalytic similarities to the platinum group metals [4] (PGMs) in several thermoand electrocatalytic reactions, such as biomass conversion, [2,5,6] hydrogen evolution and oxygen reduction, [7][8][9][10][11] and alcohol electrooxidation. [12,13] The reactivity of WC has been partially attributed to the intercalation of C to the W lattice, which gives rise to a "Pt-like" d-band electronic density states (DOS). [14] Peppernick et al. demonstrated that WC À ions exhibit isoelectronic correspondence with Pt À ions.[15] Because WC exhibits high thermal and electrochemical stability while resisting common catalyst poisons such as carbon monoxide and sulfur, [1][2][3] it has been identified as a suitable candidate to replace PGM catalysts in emerging renewable energy technologies, such as fuel cells and electrolyzers. [7][8][9][10][11][16][17][18] While there are many methods to synthesize WC nanoparticles (NPs), none of the current methods can simultaneously prevent sintering of the WC nanoparticles while also mitigating surface impurity deposition. Thus, despite the promising catalytic properties of model WC surfaces, the lack of synthesis methods to produce metal-terminated WC NPs of controlled sizes has prevented its wide-spread use as an earthabundant catalyst. [1,2,7,19] The high carburization temperatures (> ca. 700 8C) required to overcome the thermodynamic and kinetic barriers for carbon incorporation into the metal lattice induce uncontrollable particle sintering, generating particles with exceedingly low surface areas that are not suitable for commercial applications (Supporting Information , Figure S1). [1,2] Although alternative synthesis methods with unconventional heating [20][21][22][23] and carbon sources [11,17,19,24,25] have been developed to mitiga...

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Engineering Non‐sintered, Metal‐Terminated Tungsten Carbide Nanoparticles for Catalysis

2014

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“…Transition metal carbides constitute a suitable alternative for noble metal-based catalysts [16,17]. Indeed, the utilization of these materials as a replacement for noble metal will decrease the final cost of the catalyst.…”

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confidence: 99%

Metal Carbides for Biomass Valorization

Chan‐Thaw

Villa

2018

Applied Sciences

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Transition metal carbides have been utilized as an alternative catalyst to expensive noble metals for the conversion of biomass. Tungsten and molybdenum carbides have been shown to be effective catalysts for hydrogenation, hydrodeoxygenation and isomerization reactions. The satisfactory activities of these metal carbides and their low costs, compared with noble metals, make them appealing alternatives and worthy of further investigation. In this review, we succinctly describe common synthesis techniques, including temperature-programmed reaction and carbothermal hydrogen reduction, utilized to prepare metal carbides used for biomass transformation. Attention will be focused, successively, on the application of transition metal carbide catalysts in the transformation of first-generation (oils) and second-generation (lignocellulose) biomass to biofuels and fine chemicals.

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“…4,5 Due to these favorable properties, TMCs have been identified as candidates for replacing expensive PGM catalysts in emerging renewable energy technologies, such as biomass conversion, fuel cells, and electrolyzers. 6,7 To maximize catalytic activity, commercial catalysts are almost always formulated as ultrasmall nanoparticles (diameters <10 nm) dispersed on a high surface area support, such as carbon black. 8 However, the synthesis of TMCs requires temperatures higher than ~700 °C.…”

Section: Introductionmentioning

confidence: 99%

Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles

Hunt

Román‐Leshkov

2015

JoVE

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A reverse microemulsion is used to encapsulate monometallic or bimetallic early transition metal oxide nanoparticles in microporous silica shells. The silica-encapsulated metal oxide nanoparticles are then carburized in a methane/hydrogen atmosphere at temperatures over 800 °C to form silica-encapsulated early transition metal carbide nanoparticles. During the carburization process, the silica shells prevent the sintering of adjacent carbide nanoparticles while also preventing the deposition of excess surface carbon. Alternatively, the silica-encapsulated metal oxide nanoparticles can be nitridized in an ammonia atmosphere at temperatures over 800 °C to form silica-encapsulated early transition metal nitride nanoparticles. By adjusting the reverse microemulsion parameters, the thickness of the silica shells, and the carburization/nitridation conditions, the transition metal carbide or nitride nanoparticles can be tuned to various sizes, compositions, and crystal phases. After carburization or nitridation, the silica shells are then removed using either a room-temperature aqueous ammonium bifluoride solution or a 0.1 to 0.5 M NaOH solution at 40-60 °C. While the silica shells are dissolving, a high surface area support, such as carbon black, can be added to these solutions to obtain supported early transition metal carbide or nitride nanoparticles. If no high surface area support is added, then the nanoparticles can be stored as a nanodispersion or centrifuged to obtain a nanopowder. Video LinkThe video component of this article can be found at

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Reactions of oxygen-containing molecules on transition metal carbides: Surface science insight into potential applications in catalysis and electrocatalysis

Cited by 89 publications

References 195 publications

Engineering Non‐sintered, Metal‐Terminated Tungsten Carbide Nanoparticles for Catalysis

Engineering Non‐sintered, Metal‐Terminated Tungsten Carbide Nanoparticles for Catalysis

Metal Carbides for Biomass Valorization

Reverse Microemulsion-mediated Synthesis of Monometallic and Bimetallic Early Transition Metal Carbide and Nitride Nanoparticles

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