Defining a Materials Database for the Design of Copper Binary Alloy Catalysts for Electrochemical CO₂ Conversion

Abstract

While Cu electrodes are a versatile material in the electrochemical production of desired hydrocarbon fuels, Cu binary alloy electrodes are recently proposed to further tune reaction directionality and, more importantly, overcome the intrinsic limitation of scaling relations. Despite encouraging empirical demonstrations of various Cu-based metal alloy systems, the underlying principles of their outstanding performance are not fully addressed. In particular, possible phase segregation with concurrent composition changes, which is widely observed in the field of metallurgy, is not at all considered. Moreover, surface-exposed metals can easily form oxide species, which is another pivotal factor that determines overall catalytic properties. Here, the understanding of Cu binary alloy catalysts for CO reduction and recent progress in this field are discussed. From the viewpoint of the thermodynamic stability of the alloy system and elemental mixing, possible microstructures and naturally generated surface oxide species are proposed. These basic principles of material science can help to predict and understand metal alloy structure and, moreover, act as an inspiration for the development of new binary alloy catalysts to further improve CO conversion and, ultimately, achieve a carbon-neutral cycle.

Nitrogen‐Doped Graphene Quantum Dots Enhance the Activity of Bi2O3 Nanosheets for Electrochemical Reduction of CO2 in a Wide Negative Potential Region

“…Bi 2 O 3 ‐NGQDs demonstrates a more positive adsorption energy of HCOOH(ads) than that of Bi 2 O 3 , indicating that HCOOH(ads) is more easily desorbed from the surface of Bi 2 O 3 ‐NGQDs to form a stable liquid product HOOCH(aq). Clearly, the intrinsic limitation of scaling relations between the OCHO* and HCOOH(ads) was broken after the combination with NGQDs . Additionally, the enhanced adsorption strength of OCHO* intermediate on Bi 2 O 3 ‐NGQDs was also confirmed by the p ‐projected density of states (pDOS) (for details see the Supporting Information, Figure S16).…”

Entropy‐Maximized Synthesis of Multimetallic Nanoparticle Catalysts via a Ultrasonication‐Assisted Wet Chemistry Method under Ambient Conditions

“…As discussed in recent papers, the HER catalytic activity in alkaline solutions is more difficult than in acidic solution, which is ascribed to weaker H/OH‐binding and a higher energy barrier for water dissociation on the catalyst surface . Modulating the electronic and geometric structures of the catalysts is a workable strategy to enhance HER catalytic performance, as seen from the results of various shape‐controlled bimetallic nanocatalysts . The synergistic effects of the different metals in multimetallic catalysts generally exhibit enhanced performance than monometallic materials in electrocatalytic reactions.…”

Isolated Square‐Planar Copper Center in Boron Imidazolate Nanocages for Photocatalytic Reduction of CO2 to CO

“…[1a,2] To date,m uch research has been devoted to developing selective catalysts for reduction of CO 2 to CO. [3] Precious metals have been identified as promising candidates for CO 2 reduction to CO but their practical applications are still limited. [7] Besides these,i ntroducing single active site in ac atalyst has been proven to be an effective strategy to study the reactive pathway and enhance the activity for CO 2 reduction reaction (CO2RR). [5] To date,v arious Cu-based catalysts have been developed but limited product selectivity due to the presence of multiple neighboring sites for involving CO 2 reduction.…”

“…Copper as an earth-abundant metal is ac ritical metal in photosynthesis [4] and Cu-based materials have been regarded as promising catalysts for efficiently photo-or electro-catalyzing CO 2 reduction. [7] Besides these,i ntroducing single active site in ac atalyst has been proven to be an effective strategy to study the reactive pathway and enhance the activity for CO 2 reduction reaction (CO2RR). To enhance product selectivity,aconventional approach is to tailor the number of nearest neighboring accessible Cu atoms,s uch as reducing the particle size [6] or hybridizing Cu with other metals.…”