Facet-dependent electrocatalysis in the HCOOH synthesis from CO2 reduction on Cu catalyst: a density functional theory study

Electrochemical Reduction of CO2 to HCOOH over Copper Catalysts

“…When it comes to the COOH* pathway, the adsorption configuration of COOH* changes from bridge site of step edge (Figure S25c, Supporting Information) to a top site on step edge (Figure S25e, Supporting Information) with the appearance of SCN*. As shown in Figure b, the formation of COOH* is the potential limiting step in the pathway, consistent with previous studies. , Under 0 V (vs RHE), the free energy of COOH* formation (Δ G ) is 0.50 eV, and it becomes uphill to 0.78 eV with the appearance of SCN*, indicating that the COOH* pathway is inhibited. The results show that the formation of HCOOH will be promoted over Cu (211) after SCN – adsorption.…”

“…As shown in Figure 5b, the formation of COOH* is the potential limiting step in the pathway, consistent with previous studies. 19,61 Under 0 V (vs RHE), the free energy of COOH* formation (ΔG) is 0.50 eV, and it becomes uphill to 0.78 eV with the appearance of SCN*, indicating that the COOH* pathway is inhibited. The results show that the formation of HCOOH will be promoted over Cu (211) after SCN − adsorption.…”

Effects of the Catalyst Dynamic Changes and Influence of the Reaction Environment on the Performance of Electrochemical CO2 Reduction

“…[4,6,23] Besides, many of these changes and factors are intertwined, further complicate the effectiveness of catalyst discovery and reactor design. For instance, dynamic morphological changes have been observed on Cu-based catalysts, [24] the resulted roughened or smoothened surfaces are expected to cause changes in surface facets, [25] chemical states, geometric current densities, [26] and further the local pH values. [27,28] When significant pH changes occur, the ions and CO 2 concentrations within the boundary layer are altered, [29,30] which could further lead to severe CO 2 consumption and overestimation of productivity and selectivity for a given system.…”

Seeded growth of gold-based nanoscale homojunctions via controlled etching regrowth and their applications for methanol oxidation reaction

“…8 When noble metal nanocrystals take the form of homojunction, there could arise several structural advantages that can be difficult to achieve for an integrated counterpart: i) despite the similarity in elemental composition, the two blocks could adopt different structural features, including crystal phase, polyhedral shapes, and/or dominant exposed facets. The potential synergetic effects between these characters, which effectively integrate the multiple advantages of each component, could be expected; [9][10][11][12] ii) the boundary region present between the adjacent blocks can work as an ideal metal-metal interfacial site to allow the atoms to stay in a coordination unsaturated state, which is of great importance for the absorption or direct chemical reactions to generate new species. [13][14][15][16][17][18][19] Unlike the twin defects that only involves the change in atomic packing direction, the rationallydesigned metal-metal interface can apply comprehensive regulation of the spatial arrangement of atoms and surface electronic structure of the electrocatalyst, which are helpful to expedite kinetics in electrocatalysis; 20 iii) by constructing a homojunction structure, the variation of overall particle shape from isotropy to anisotropy contributes to the generation of multiple localized surface plasmon resonance (LSPR) absorption bands due to the increase in surface electron oscillation modes.…”