Decomposition pathways of C2 oxygenates on Rh-modified tungsten carbide surfaces

Abstract

Ethanol decomposition on tungsten monocarbide (WC) and Rh-modified WC was investigated using ultrahigh vacuum (UHV) surface science experiments and density functional theory (DFT) calculations. DFT calculations indicated that the binding energies of ethanol and its decomposition intermediates on WC(0001) were modified by Rh, with Rh/WC (0001) showing similar values to those on Rh(111). Through temperature-programmed desorption (TPD) experiments on polycrystalline WC and Rh-modified WC, it was shown that the selectivity for ethanol decomposition was different on these surfaces. On WC, the C-O bond of ethanol was preferentially broken to produce ethylene; on Rh-modified WC, the C-C bond was broken to produce carbon monoxide and methane. Furthermore, high-resolution electron energy loss spectroscopy (HREELS) was used to determine likely surface intermediates. On Rh-modified WC, ethanol first formed ethoxy through O-H scission, then reacted through an aldehyde intermediate to form the C1 products.

Tungsten Carbide‐Based Materials for Electrocatalytic Water Splitting: A Review

“…On Rh-modified WC, ethanol first formed ethoxy through OÀ H scission, then reacted through an aldehyde intermediate to form the C 1 products. [210] In short, addressing the current issues in nanomaterial design and electrocatalysis requires a multidisciplinary approach involving experimental techniques, advanced characterization, and computational modeling. A detailed understanding of the nanoscale behavior of WC nanoparticles and their integration into larger systems is essential for optimizing catalytic performance.…”

Syngas Conversion to C2 Species over WC and M/WC (M = Cu or Rh) Catalysts: Identifying the Function of Surface Termination and Supported Metal Type

“…For example, Yao et al 57 synthesized Cu/ WC catalyst, in which Cu/CF(Cu foam) was first obtained by a wet chemical method and an electrochemical method, and then the WC layer was directly deposited onto Cu/CF by the process of magnetron sputtering. Kelly et al 58 prepared Rh/ WC catalyst via the physical vapor deposition; specifically, the Rh wire was heated under a desirable temperature to evaporate Rh atoms onto WC catalyst. Meanwhile, the coverage of Rh atoms was estimated using the Rh/W AES peak intensity ratio.…”

LDRD 2014 Annual Report: Laboratory Directed Research and Development Program Activities

“…These results were instrumental in receiving Department of Energy funding for ongoing support of the Chen group's efforts at BNL [1], and contributed to an initial publication [2]. The Chen group also investigated routes for conversion of C2 oxygenate fuels, which can be derived from biomass and are another path to sustainably recycle CO 2 into fuels [3], [4].…”