Seeded Growth of Gold–Copper Janus Nanostructures as a Tandem Catalyst for Efficient Electroreduction of CO₂ to C₂₊ Products

Abstract

Gold–copper (Au‐Cu) Janus nanostructures (Au‐Cu Janus NSs) are successfully prepared using N‐oleyl‐1,3‐propanediamine as capping agent and Cu(acac)2 as the precursor in a typical seeded growth strategy. By preferably depositing Cu atoms on one side of concave cubic Au seeds, the Cu part gradually grows larger as more Cu precursors are added, making the size tuning feasible in the range of 74–156 nm. When employed as an electrocatalyst for electrochemical CO2 reduction (CO2RR), the Au‐Cu Janus NSs display superior performance to Au@Cu core‐shell NSs and Cu NPs in terms of C2+ products selectivity (67%) and C2+ partial current density (−0.29 A cm–2). Combined experimental verification and theoretical simulations reveal that CO spillover from Au sites to the nearby Cu counterparts would enhance CO coverage and thus promote C–C coupling, highlighting the unique structural advantages of the Au‐Cu Janus NSs toward deep reduction of CO2. The current work provides a facile strategy to fabricate tandem catalyst with a Janus structure and validates its structural advantages toward CO2RR, which are of critical importance for the rational design of efficient CO2RR catalyst.

Surface-Regulated Platinum–Copper Nanoframes in Electrochemical Reforming of Ethanol for Efficient Hydrogen Production

“…34,35 As for Cu, Cu 2p 3/2 and Cu 2p 1/2 can be also divided into two doublets of Cu 0 and Cu 2+ . 36,37 Compared with PtCu ND/C, the Pt 4f 7/2 peak of the PtCu NF/C slightly shifts to the higher value (Figure 4a), while the Cu 2p binding energy in PtCu NF/C shifts to the lower binding energy (Figure S27), indicating that the electron transfer and electronic structure changes of Pt and Cu occurred after the dealloying process. Besides, the change in the electronic structure is also likely associated with the abundant high-index facets on the PtCu NF/C surface, which would provide more possibilities for the adsorption, activation, and dissociation of intermediates, resulting in enhanced catalytic performance.…”

“…In order to figure out the unique catalytic activity of PtCu NF/C, we first used XPS to analyze their electronic structure (Figures , S26 and S27). It can be seen in Figure a that there are two peaks belonging to the states of Pt 4f 7/2 and Pt 4f 5/2 in the Pt 4f spectrum of PtCu NF/C, and each peak can be further divided into two double peaks related to Pt 0 and Pt 2+ , respectively. , As for Cu, Cu 2p 3/2 and Cu 2p 1/2 can be also divided into two doublets of Cu 0 and Cu 2+ . , Compared with PtCu ND/C, the Pt 4f 7/2 peak of the PtCu NF/C slightly shifts to the higher value (Figure a), while the Cu 2p binding energy in PtCu NF/C shifts to the lower binding energy (Figure S27), indicating that the electron transfer and electronic structure changes of Pt and Cu occurred after the dealloying process. Besides, the change in the electronic structure is also likely associated with the abundant high-index facets on the PtCu NF/C surface, which would provide more possibilities for the adsorption, activation, and dissociation of intermediates, resulting in enhanced catalytic performance.…”

The Nature of Interfacial Catalysis over Pt/NiAl2O4 for Hydrogen Production from Methanol Reforming Reaction

“…People are more familiar with the discussions focused on the diffusion (or spillover, which is defined as the transport of one type of species adsorbed or formed on a specific surface (or site) to another, which does not adsorb or form this kind of species under the same conditions) of some small molecules. For instance, H 2 spillover was widely investigated in a variety of systems. − CO − and oxygen atoms or molecules − have also been reported; in addition, the spillover of some functional groups were also well discussed in some previous studies, e.g., methoxyl , and formate . Therefore, the identification of the sites for adsorption and reaction is essential for understanding the active components for methanol reforming.…”

“…41−44 CO 45−47 and oxygen atoms or molecules 48−53 have also been reported; in addition, the spillover of some functional groups were also well discussed in some previous studies, e.g., methoxyl 54,55 and formate. 45 Therefore, the identification of the sites for adsorption and reaction is essential for understanding the active components for methanol reforming.…”

Fabrication of Gold-Based “Sphere-on-Plate” Hybrid Nanostructures with Dual Plasmonic Absorptions Covering Visible and Near-Infrared II Windows via the Volmer–Weber Growth Mode

“…Hybrid noble metal nanocrystals are of great interest due to the effective coupling between the constitutional components. − Owing to the maximized exposures of each component and abundant supply of interfaces, the hybrid nanostructures can exhibit intriguing physicochemical properties. − Therefore, it is of great value to study how to fabricate noble metal nanostructures with hybrid spatial configuration of each component . To achieve such a goal via seeded growth, the Volmer–Weber (VW) growth mode is usually expected to be involved. − It is also known as “island growth”, where the growth occurs as governed by the lattice strain between the substrate and deposited material. , However, it is difficult to expect if the deposited atoms have the same or similar lattice structure and spacing as the substrate atom, where the growth would typically be conducted via the Frank–van der Merwe (FM) mode, as a perfect wetting can be present in the interface. − In this case, the surface modification of the substrate material becomes crucial to provide the source for lattice strain.…”