The mechanism of HCOOH decomposition on Pd(111) surface leading to the formation of CO 2 and CO has been systematically investigated to identify the preference of CO 2 or CO as the dominant product. Here, we present the main results obtained from periodic, self-consistent density functional theory calculations. Four possible pathways of HCOOH decomposition, initiated by the activation of the O− H, C−H, and C−O bonds of HCOOH, as well as the activation of simultaneous C−H and C−O bonds of HCOOH, have been proposed and discussed. Then, the effects of coadsorbed H 2 O and its coverage on the decomposition of HCOOH have been also considered. Our results show that CO 2 is preferentially formed as the dominant product of HCOOH decomposition on Pd(111) surface via a dual-path mechanism, which involves both the carboxyl (trans-COOH) and formate (bi-HCOO) intermediates, along with alternative bond-breaking possible steps in those intermediates. The dehydrogenation of HCOOH on Pd surface is a vital process for CO 2 formation. Further, the coadsorbed H 2 O and its coverage play an important role in the decomposition of HCOOH, and the preferred catalytic pathway of CO 2 formation is qualitatively dependent on surface H 2 O coverage. Therefore, our results would at the microscopic level provide insights into the mechanism, energetics, and possible reactive intermediates of HCOOH decomposition regarding the preference of CO 2 formation as the dominant product for the catalytic reactions involving HCOOH and for a direct HCOOH fuel cell on Pd system.

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Density functional theory (DFT) analysis is used to shed light on the intricate effects of the Co 2 C and Co/Co 2 C catalyst crystal facets on the selectivity of the C 2 oxygenate and hydrocarbon formation in Fischer−Tropsch synthesis. Three representative low-index Co 2 C (101), (110), and (111) surfaces, varying in surface energy from low and medium to high, are model examples of different Co 2 C exposed crystal facets. Since CH x (x = 1−3), CO, and H species are the key intermediates critical to the C 2 oxygenate selectivity, all Fischer−Tropsch reactions related to CH x (x = 1−3) species, including CO insertion into CH x (x = 1−3) and CH x + CH y (x, y = 1−3) coupling to form C 2 species (C 2 H x and C 2 H x O), as well as the hydrogenation and dissociation of CH x (x = 1−3) to form C 1 species (CH 4 and C), are used as examples examined at a typical FTS temperature of 493 K. On Co 2 C (101) and ( 110) surfaces, CH and CH 2 species are dominant form of the CH x species, CH self-coupling to C 2 H 2 and CH coupling with CH 2 to CH 2 CH is dominant C 2 species. However, on a Co 2 C (111) surface, only CH monomer is a dominant CH x (x = 1−3) species, and CO insertion into CH to form CHCO is a dominant C 2 species. CH 4 and C production on these three surfaces is impossible. These results show that C 2 species formation, rather than C 1 species, is a preferable pathway on different Co 2 C crystal facets in FTS reactions. Moreover, the C 2 selectivity, quantitatively estimated from the effective barrier difference, is found to be sensitive to the Co 2 C crystal facet. The Co/Co 2 C (111) interface catalyst is more favorable for C 2 oxygenate formation in comparison to the pure Co 2 C (111) catalyst, whereas the Co/Co 2 C (110) and Co/Co 2 C (101) interface catalysts are unfavorable for C 2 oxygenate formation in comparison to the pure Co 2 C (110) and (101) catalysts. Therefore, for the FTS over Co 2 C and Co/Co 2 C catalysts, the Co 2 C (111) crystal facet is found to have an unexpectedly high selectivity for C 2 oxygenates, whereas the Co 2 C ( 101) and ( 110) crystal facets are found to have a high selectivity toward C 2 hydrocarbons. The results mean that controlling the crystal facets of Co 2 C catalysts using well-defined preparation methods can be an effective tool to tune the FTS selectivity toward the most desirable products.

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CO hydrogenation to higher alcohols (C2+OH) provides a promising route to convert coal, natural gas, shale gas, and biomass feedstocks into value-added chemicals and transportation fuels. However, the development of nonprecious metal catalysts with satisfactory activity and well-defined selectivity toward C2+OH remains challenging and impedes the commercialization of this process. Here, we show that the synergistic geometric and electronic interactions dictate the activity of Cu0–χ-Fe5C2 binary catalysts for selective CO hydrogenation to C2+OH, outperforming silica-supported precious Rh-based catalysts, by using a combination of experimental evidence from bulk, surface-sensitive, and imaging techniques collected on real and high-performance Cu–Fe binary catalytic systems coupled with density functional theory calculations. The closer is the d-band center to the Fermi level of Cu0–χ-Fe5C2(510) surface than those of χ-Fe5C2(510) and Rh(111) surface, and the electron-rich interface of Cu0–χ-Fe5C2(510) due to the delocalized electron transfer from Cu0 atoms, facilitates CO activation and CO insertion into alkyl species to C2-oxygenates at the interface of Cu0–χ-Fe5C2(510) and thus enhances C2H5OH selectivity. Starting from the CHCO intermediate, the proposed reaction pathway for CO hydrogenation to C2H5OH on Cu0–χ-Fe5C2(510) is CHCO + (H) → CH2CO + (H) → CH3CO + (H) → CH3CHO + (H) → CH3CH2O + (H) → C2H5OH. This study may guide the rational design of high-performance binary catalysts made from earth-abundant metals with synergistic interactions for tuning selectivity.

The possible formation pathways of CH x (x = 1–3) and C–C chain involved in C2 oxygenate formation from syngas on an open Cu(110) surface have been systematically investigated to identify the preference mechanism of CH x (x = 1–3) and C–C chain formation. Here, we present the main results obtained from periodic density functional calculations. Our results show that all CH x (x = 1–3) species formation starts with CHO hydrogenation; among them, CH x (x = 2, 3) are the most favored monomers, however, CH3OH is the main product from syngas on the Cu(110) surface, and the formation of CH x (x = 1–3) cannot compete with CH3OH formation. Further, on the basis of the favored monomer CH x (x = 2, 3), we probe into the C–C chain formation of C2 oxygenates by CO or CHO insertion into CH x (x = 2, 3), as well as the hydrogenation, dissociation, and coupling of CH x (x = 2, 3), suggesting that CO insertion into CH2 to form C2 oxygenates is the dominant reaction for CH2 on the Cu(110) surface with an activation barrier of 44.5 kJ·mol–1; however, for CH3, CH3 hydrogenation to CH4 is the dominant reaction on the Cu(110) surface with an activation barrier of 67.5 kJ·mol–1. As a result, to achieve high productivity and selectivity for C2 oxygenates from syngas, Cu has to get help from the promoters, which should be able to boost CH2 formation and/or suppress CH3OH and CH3 formation. The present study provides the basis to understand and develop novel Cu-based catalysts for C2 oxygenate formation from syngas.

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