First-Principles Investigation of the Electrocatalytic Reduction of CO₂ on Zirconium-Based Single-, Double-, and Triple-Atom Catalysts Anchored on a Graphitic Carbon Nitride Monolayer

Abstract

Conversion of carbon dioxide (CO2) with the help of an appropriate electrocatalyst with high stability, low onset potential, and exceptional selectivity is still one of the great tasks in the electrocatalytic reduction of CO2 to valuable chemicals. Herein, by means of systematic first-principles simulations, we investigate the CO2 reduction reaction (CO2RR) activity of zirconium-based single-, double-, and triple-atom (Zr n @C2N; n = 1–3) catalysts anchored on a graphitic carbon-nitride monolayer. In tune with the Sabatier principle, our results reveal that a moderate CO2 binding is vital for a low onset potential for the CO2RR. Consequently, based on rigorous free energy calculations, the Zr-based single-atom catalyst (SAC) is found to be most effective to convert CO2 to valuable products such as HCOOH and CH3OH. It is worth noting that CO2 reduction to HCOOH is spontaneous via the *HCOO intermediate on Zr1@C2N and involves a low onset potential of −0.23 V with respect to the reversible hydrogen electrode from the *COOH intermediate. Among all the catalysts evaluated computationally, the Zr SAC further reveals the lowest onset potential of −0.89 V for CH3OH formation. The results show that the Zr-based catalysts especially Zr1@C2N are found to effectively suppress the competitive hydrogen evolution reaction and promote the CO2RR. Moreover, all three catalysts exhibit high kinetic and thermal stability with negligible distortion due to which their structures can be retained very well up to 600 K. Thus, the current work may provide effective catalyst-design strategies for enhancing the electrocatalytic CO2RR performance of Zr-based materials.

Understanding the activity of single atom catalysts for CO2 reduction to C2 products: A high throughput computational screening

“…Moreover, the inclusion of the solvent effect has a negligible impact on the limiting potential values with À1.48, À2.28 and À2.20 V Cu@C 2 N, Fe@C 2 N, and Cr@C 2 N respectively, which is in line with earlier reported results. 32,49,50 We also computed the kinetic barriers for the PDS using the climbing image nudged elastic band calculations, as shown in Fig. S3 (ESI †).…”

“…[26][27][28][29][30] Owing to these reasons, many interesting experimental and theoretical research works have surfaced to better understand and screen the activity of single atom catalysts for CO 2 reduction to C 1 products such as CO and HCOOH. 9,10,31,32 Although SACs are widely used for CO 2 RR to C 1 products, the formation of multicarbon products on SACs is still a challenge and more work needs to be done in this direction. Recently some studies have been carried out wherein it has been revealed that Cu-based SACs can be utilized for the reduction of CO 2 to C 2 products.…”

Boosting CO2 Activation and Reduction by Engineering the Electronic Structure of Graphitic Carbon Nitride through Transition Metal-Free Single-Atom Functionalization

“…Since the discovery of the stable two-dimensional graphitic phase of C 3 N 4 by Wang et al, an entire group of stable carbon nitride materials has been explored with applications in photocatalysis, − sensing/bioimaging, , and electrocatalysis . Among the carbon–nitrogen materials, the unique physical and electronic properties of g-C 2 N such as high thermal and chemical stability, enhanced specific surface area, and uniform distribution of pores with pyrazinic sp 2 nitrogen atoms make it an attractive supporting material for single- and double-atom catalysts.…”

An effective strategy for CO2 reduction to C1 products using Cu-embedded MoS2 electrocatalyst: DFT study

“…So, it is verified that the MoS 2 SAC with embedded Cu shows an excellent catalytic activity for the reduction of CO 2 to CH 4 (via optimized path 5) compared to the pristine MoS 2 . In order to highlight our result, we have shown a comparison of our limiting potential with that of other reported CO 2 RR catalysts, such as Fe-C 3 N 4 , 61 Zr@C 2 N, 65 Cu (111) and Cu-phosphorene, 64 in Fig. 7.…”