Beyond d Orbits: Steering the Selectivity of Electrochemical CO₂ Reduction via Hybridized sp Band of Sulfur‐Incorporated Porous Cd Architectures with Dual Collaborative Sites

Abstract

serious global warming and climate deterioration. As a promising strategy, electrochemical CO 2 reduction reaction (ECRR) not only hinders the increased CO 2 emission, but also favors the generation of high value-added chemical fuels. [1,2] Especially, ECRR can be supplied by renewable energy source such as solar and wind energy, thus exhibiting great potential for practical applications with environmental and economic benefits. [3] However, it is still an enormous challenge to conduct efficient CO 2 electroreduction with high selectivity owing to the high energy barriers of activating stable CO 2 molecules with strong chemical bond and the intense competition between ECRR and thermodynamically favorable hydrogen evolution reaction (HER) in aqueous media. [2-4] Over the past few decades, transitional metal (Au, Ag, Pd, Zn, Cu) based electrocatalysts have been extensively conducted for efficiently catalyzing CO 2 reduction. [5,6] It is well acknowledged that the narrow d band is of great significance for strong interaction with adsorbates, contributing to split of bonding states. [7] Accordingly, the d band center is recognized as the key descriptor of transitional metals (TMs) reactivity toward electrocatalysis of CO 2 molecules. [8] Notwithstanding the superior ECRR activities of TMs with *COOH affinity and high CO selectivity, the intrinsic scaling relationship in d band model has greatly restricted its versatility for tunable products generation. [9,10] Intriguingly, the metal-free carbon-based materials have displayed excellent availability for various reduction pathways, which disturbs the linear scaling limitation due to the absence of d orbits. [3] For instance, N-doped carbon (NC) with enormous edge sites exhibits excellent selectivity of CO and multicarbon fuels. [11] In addition, basic pyridinic nitrogen in NC can serve as the active sites for the efficient formation of formate. [12,13] Enlightened by the flexible selectivity of carbonbased electrocatalysts, the deliberate utilization of s and p band may be a potent strategy for effectively steering the selectivity of TMs. Apart from the inherent natures of electrocatalysts, the outer morphology also plays a pivotal role in tailoring the efficiency of electrocatalytic CO 2 reduction. Since the superb accessibility of porous configuration with gas molecules, it is peculiarly Electrochemical CO 2 reduction is regarded as a promising strategy for the sustainable conversion of greenhouse gas. However, it still remains a significant challenge to manipulate the selectivity and activity. Herein, amorphous and porous Cd modified by sulfur (P-Cd|S) is synthesized by a p-block sulfur dopant. In comparison with unmodified Cd metal, the P-Cd|S architecture exhibits superior activity for selective CO generation, indicating that the sulfur dopant enables a selectivity shift from formic acid to CO. The high selectivity of P-Cd|S is partially ascribed to the local alkalization and suppression of hydrogen evolution as indicated by the finite element analysis. In-depth m...

A Tandem Strategy for Enhancing Electrochemical CO2 Reduction Activity of Single‐Atom Cu‐S1N3 Catalysts via Integration with Cu Nanoclusters

“…The redshift of vibrational frequencies for the adsorbed intermediates at larger overpotentials was induced by the changing of the local electric field near the surface, known as the electrochemical Stark effect. [23] Subsequently, DFT calculations were carried out to study the effects of Cu-S coordination and Cu clusters at the molecular level. To provide a plausible explana- In summary, we have demonstrated a Cubased tandem catalyst Cu-S 1 N 3 /Cu x with co-existed atomically dispersed Cu-S 1 N 3 sites and Cu clusters as a powerful CO 2 -to-CO conversion electrocatalyst.…”

Helical copper-porphyrinic framework nanoarrays for highly efficient CO2 electroreduction

“…The electrocatalytic CO 2 reduction is a prospective strategy for the transformation of CO 2 into fuels and chemicals. In this strategy, CO 2 is used as a raw material to produce valuable products, which can reduce greenhouse gas CO 2 and greatly contribute to solving environmental and energy crises [1][2][3][4][5]. With CO 2 electroreduction, it is usually more difficult to transform multi-carbon products than simple C 1 products [6][7][8].…”

Synergistically electronic tuning of metalloid CdSe nanorods for enhanced electrochemical CO2 reduction

“…Therefore, the above results suggested that the integration of Ag doping and Se vacancies in the CdSe nanorods synergistically enhanced the selectivity to CO. Notably, as shown in Table S2, the Ag-doped CdSe nanorods exhibited a considerable j CO of 19.68 mA cm −2 with FE of 91%, outperforming most related electrocatalysts for CO production [6,17,[40][41][42][43][44][45]. In addition, the durability of the pristine CdSe and 3.1% Ag-CdSe nanorods for CO 2 electroreduction to CO was examined by current-time (I-t) measurements at the potentiostatic of −1.15 V vs. RHE (Fig.…”