Preparation of Amorphous SnO₂‐Encapsulated Multiphased Crystalline Cu Heterostructures for Highly Efficient CO₂ Reduction

Abstract

Among various kinds of heterostructures, the metal@semiconductor heterostructures with a core-shell or yolk-shell architecture have received great attention because of their unique physicochemical properties and promising catalytic application. [5,6] In core-shell heterostructures, the interaction between the core and shell could enhance their catalytic performance. [7][8][9] Normally, if there is an entirely empty void between the core and shell, a yolk-shell heterostructure is obtained. The interior void in the yolk-shell heterostructure may act as a reactor that allows the direct contact of the metal yolk with the reactant during a catalytic reaction. However, if a partial void exists between the core and shell, a hemicapsule heterostructure is constructed, in which the core partially contacts the shell. This unique architecture might endow the hemicapsule heterostructure with merits of both the core-shell and yolk-shell heterostructures and thus show great potential for promising catalytic applications. However, the metal@semiconductor hemicapsule heterostructures have been seldom studied due to their difficult preparation. [10,11] In particular, it is still very challenging for the precise structural Controlling the architectures and crystal phases of metal@semiconductor heterostructures is very important for modulating their physicochemical properties and enhancing their application performances. Here, a facile one-pot wet-chemical method to synthesize three types of amorphous SnO 2 -encapsulated crystalline Cu heterostructures, i.e., hemicapsule, yolk-shell, and core-shell nanostructures, in which unconventional crystal phases (e.g., 2H, 4H, and 6H) and defects (e.g., stacking faults and twin boundaries) are observed in the crystalline Cu cores, is reported. The hemicapsule Cu@SnO 2 heterostructures, with voids that not only expose the Cu core with unconventional phases but also retain the interface between Cu and SnO 2 , show an excellent electrocatalytic CO 2 reduction reaction (CO 2 RR) selectivity toward the production of CO and formate with high Faradaic efficiency (FE) above 90% in a wide potential window from −1.05 to −1.55 V (vs reversible hydrogen electrode (RHE)), and the highest FE of CO 2 RR (95.3%) is obtained at −1.45 V (vs RHE). This work opens up a new way for the synthesis of new heterostructured nanomaterials with promising catalytic application.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adma.202201114.

Sn Dopants with Synergistic Oxygen Vacancies Boost CO2 Electroreduction on CuO Nanosheets to CO at Low Overpotential

“…A slight Cu + signal was observed in the XPS spectrum, which might be related to the presence of numerous oxygen vacancies in CuO . As shown in Figure B, the characteristic peaks appearing at 486.58 and 495.03 eV corresponded closely to the Sn 4+ oxidation state, confirming the successful doping of the Sn element . Besides, the mass content of Sn calculated by the XPS spectrum was approximately 2.97 atom %, which was further determined by the experimental results of inductively coupled plasma optical emission spectroscopy (ICP-OES, Table S2, Supporting Information).…”

“…26 As shown in Figure 2B, the characteristic peaks appearing at 486.58 and 495.03 eV corresponded closely to the Sn 4+ oxidation state, confirming the successful doping of the Sn element. 27 Besides, the mass content of Sn calculated by the XPS spectrum was approximately 2.97 atom %, which was further determined by the experimental results of inductively coupled plasma optical emission spectroscopy (ICP-OES, Table S2, Supporting Information). The atomic ratio of Cu and Sn was 96.85:3.15 in the as-prepared V o -CuO(Sn) nanosheet through quantitative analysis.…”

Metal‐Based Aerogels Catalysts for Electrocatalytic CO2 Reduction

“…[23][24][25][26][27][28][29][30][31] From an energy perspective, CO 2 , as an economical and readily available C 1 gas, can be used to produce a variety of energy-intensive carbon-based fuels, which would reduce global society's dependence on fossil energy sources. [32][33][34][35][36][37][38] However, the conventional catalysts such as metals, transition metal oxides and sulfides have weak adsorption capacity for CO 2 and poor catalytic performance, which lead to poor selectivity of the reduction products. [39][40][41][42][43][44][45] Therefore, efforts should be made to develop a new and efficient catalyst for CO 2 reduction.…”

Strain-Regulated Pd/Cu Core/Shell Icosahedra for Tunable Syngas Electrosynthesis from CO2

“…Using CO 2 as a potential carbon source to obtain high-value chemical products through electrochemical catalysis is an ideal strategy of CO 2 conversion, which can directly convert CO 2 into diverse energy materials, thus closing the man-made carbon cycle. − At present, most of the research on the CO 2 reduction reaction (CO 2 RR) is mainly to pursue high Faradaic efficiency (FE) and yield of products such as methane, methanol, formate, and multi-carbon products. − Therefore, it is significant to develop high-performance electrocatalysts for the CO 2 RR and suppress the side reaction of the hydrogen evolution reaction (HER), which is generally performed under cathodic conditions in an aqueous electrolyte. , Although significant efforts have been made to prohibit the HER by designing electrocatalysts, the low selectivity of the CO 2 RR remains a key challenge.…”