Tuning Gold Nanoparticles with Chelating Ligands for Highly Efficient Electrocatalytic CO₂ Reduction

Abstract

Capped chelating organic molecules are presented as a design principle for tuning heterogeneous nanoparticles for electrochemical catalysis. Gold nanoparticles (AuNPs) functionalized with a chelating tetradentate porphyrin ligand show a 110-fold enhancement compared to the oleylamine-coated AuNP in current density for electrochemical reduction of CO to CO in water at an overpotential of 340 mV with Faradaic efficiencies (FEs) of 93 %. These catalysts also show excellent stability without deactivation (<5 % productivity loss) within 72 hours of electrolysis. DFT calculation results further confirm the chelation effect in stabilizing molecule/NP interface and tailoring catalytic activity. This general approach is thus anticipated to be complementary to current NP catalyst design approaches.

Electrochemical Conversion of CO2 to Syngas with Controllable CO/H2 Ratios over Co and Ni Single‐Atom Catalysts

“…Moreover, Ni‐NC showed high J(CO) values such as circa 12.1 mA cm −2 at −0.7 V RHE and circa 56 mA cm −2 at −1.0 V RHE (Supporting Information, Figure S13 b), which was better than Au NPs (7.9 mA cm −2 at −0.7 V RHE ) and immobilized Ag NPs (ca. 8.0 mA cm −2 at −1.0 V RHE ) . In comparison, both Co/NC and Ni/NC nanoparticle and NC metal‐free catalysts exhibited negligible CO 2 RR activity (Supporting Information, Figures S14–S16).…”

Morphology‐Controlled Bi2O3 Nanoparticles as Catalysts for Selective Electrochemical Reduction of CO2 to Formate

“…However, too much loading amount makes the catalyst layer too thick, leading to easy cracking and falling of the catalyst from the electrode as well as larger electric resistance, which is in accord with SEM results in Figure 2, thus resulting in lower catalytic activity for CO 2 electroreduction. [30,[54][55][56] According to the previous investigations, [2,16,37,40] a general mechanism of CO 2 electroreduction to formate is illustrated in Equations (1-4). To probe the mechanism of CO 2 electroreduction, an electrokinetic study is necessary.…”

“…Up to now, various methods, including chemical methods, [1] electrochemical methods, [2][3][4] and photochemical methods, [5,6] have been developed to convert and utilize carbon dioxide. Among these methods, an electrochemical method has attracted growing attention [7][8][9][10][11][12][13][14][15][16] since it could effectively convert CO 2 into valuable chemicals under mild conditions [17][18][19] and provide an effective and simple route for the energy storage (such as geothermal energy, solar energy and wind power). Formic acid is one of important products from the electro-reduction of CO 2 .…”

Strategies for Designing Nanoparticles for Electro‐ and Photocatalytic CO2 Reduction

“…Liu et al. employed tetradentate porphyrins to Au NPs capped with oleylamine via ligand exchange to stabilize the *COOH intermediate and expose more active sites . Chang and Yang et al.…”

“…[18b] Liu et al employed tetradentatep orphyrinst o Au NPs capped with oleylamine via ligand exchange to stabilize the *COOHi ntermediate and expose more active sites. [24] Chang and Yang et al introduced N-heterocyclicc arbenes (NHCs) (Figure 3(b)), for which Ta fel plots revealed that Au-NHC bonds destabilized the Au surface and formed af ast preequilibrating initial electron transfer step. [25] Surfacea nionsc an also play ac rucial role.…”