Single Nickel Atom-Modified Phosphorene Nanosheets for Electrocatalytic CO₂ Reduction

Abstract

Nowadays, carbon dioxide (CO 2 ) produced by global energy consumption far exceeds what the environment can absorb. So, the world is seeking a way to control and reduce CO 2 emissions. The electrocatalytic CO 2 reduction reaction (CRR) can effectively convert this greenhouse gas into energy sources, thus providing a method to solve CO 2 emission and energy crisis issues. However, only quite limited catalysts are capable of converting CO 2 into high-value C1 products. Herein, four structures of single Ni atom-modified phosphorene, as an electrocatalyst for the CRR, have been studied by first-principles calculations based on density functional theory (DFT). The results show that a single Ni atom adsorbed on monoatomic defective phosphorene (Ni-D-BP) has higher long-term activity and stability, and better CRR selectivity against the hydrogen evolution reaction (HER). In particular, Ni-D-BP shows good selectivity for HCOOH with a limiting potential of −0.31 V. The production of CH 3 OH and CH 4 has the same limiting potential of −0.98 V, indicating that Ni-D-BP also has good catalytic properties for CH 3 OH or CH 4 production. This study can reveal the mechanism of the CRR for single Ni atom-modified phosphorene-based catalysts and provide a way to design electrocatalysts for the CRR on the atomic scale.

Single Atom Catalysts for Selective Methane Oxidation to Oxygenates

“…Similarly, P atoms can also coordinate with other metallic centers making them suitable candidates for the supporting SA centers. 412 Luo et al synthesized gold SA decorated BP nanosheets (Au 1 /BP nanosheets) by injecting HAuCl 4 precursor in exfoliated BP suspension. 413 The color mapped HAADF-STEM image of 0.2 wt % Au 1 /BP nanosheets, displayed the atomic distribution of Au on the sheets (Figure 27a).…”

“…These P atoms are easily oxidized under air/oxygen/water to form P–O and PO dangling bonds. Similarly, P atoms can also coordinate with other metallic centers making them suitable candidates for the supporting SA centers . Luo et al synthesized gold SA decorated BP nanosheets (Au 1 /BP nanosheets) by injecting HAuCl 4 precursor in exfoliated BP suspension .…”

Boosting Electrocatalytic Reduction of CO2 to HCOOH on Ni Single Atom Anchored WTe2 Monolayer

“…Compare to other metals anchored WTe 2 in this study and other CO 2 RR catalysts reported in the literature, Ni@WTe 2 possesses better catalytic performance to produce HCOOH (Table S1, Supporting Information). [46][47][48][49][50]…”

Pd speciation on black phosphorene in a CO and C2H4 atmosphere: a first-principles investigation

“…18 Preformed Ag, Au, Ni, Pd and Pt nanoparticles were loaded onto few-layer phosphorene and the observed superior performance in gas sensing, selective hydrogenation, oxidation and photocatalysis was attributed to the metal/phosphorene contact. [19][20][21][22][23][24] Phosphorene based single atom catalysts (SACs) were also proposed to be efficient in the partial oxidation of methane, 25 electrocatalytic nitrogen, CO and CO 2 reductions, [26][27][28][29][30][31] hydrogenation, 32 CO oxidation, 33,34 oxygen reduction/evolution and hydrogen evolution, 35 etc. However, the reported approaches for the fabrication of phosphorene based SACs are still limited to the atomic layer deposition with the reaction of high energy precursors with the phosphorene support that may result in defective or doped phosphorene, and the wet chemistry approach through liquid phase reduction of precursors, but further treatment is required.…”