Bismuth Incorporation in Palladium Hydride for the Electrocatalytic Ethanol Oxidation with Enhanced CO Tolerance

Abstract

Introducing nonmetal and oxophilic metal into palladium (Pd)-based catalysts is beneficial for boosting electrocatalysis, especially regarding the improvement of mass activity (MA) and CO tolerance. Herein, the stable bismuth-doped palladium hydride (Bi/PdH) networks have been successfully fabricated through a simple one-step method. The intercalation of interstitial H atoms expands the lattice of Pd, and the doping of oxophilic metal Bi restrains the adsorption of poisonous intermediates on the surface of Pd, thereby improving the activity and durability of the as-prepared catalysts in the ethanol oxidation reaction (EOR). The obtained Bi/ PdH networks manifest a remarkable MA of 8.51 A•mg Pd −1 , which is 11.18 times higher than that of commercial Pd/C (0.76 A•mg Pd −1). The CO-stripping analysis results indicate that Bi doping can significantly prohibit CO adsorption on the surface of the Bi/PdH networks. The density functional theory (DFT) calculations also reveal that Bi doping enhances the OH* adsorption on the catalyst surface and mitigates the interaction between Pd and CO* intermediates, providing deeper insights into the origin of the enhanced EOR activity and CO tolerance. This work describes an impactful path for producing high-performance and durable PdH-based nanocatalysts.

Advances in Strain‐Induced Noble Metal Nanohybrids for Electro‐Catalysis: From Theoretical Mechanisms to Practical Use

“…For instance, the differential precipitation of Pt and Pd results in the reduction of Pd ions into Pd metal cores due to their lower reduction potential. [54] Additionally, other structures such as porous Pd@PdPt core/ shell nanocrystals, [55] bismuth-doped palladium hydride (Bi/PdH) networks, [56] and PtÀ Nd co-doped Ti/SnO 2 -Sb nanosphere electrodes [57] have been successfully fabricated using a one-step method. In the pursuit of surfactant-free preparation, Pd-based heterostructures composed of W-doped Pd nanosheets (Pd-PdW HSs) were synthesized using a one-pot polymeric surfactant-free epitaxial growth method.…”

“…[100] Furthermore, the intercalation of interstitial hydrogen atoms expands the lattice of Pd, and doping with the oxophilic metal bismuth restrains the adsorption of poisonous intermediates on the Pd surface. [56] Similar alloying techniques have been extensively studied, with Bandarenka creating a volcano plot for PtM alloys, correlating the Oxygen Reduction Reaction (ORR) activity with various parameters [94] (Figure 5c).…”

Electronic state regulation induced by the strong metal–support interactions boosts the performance of alcohol oxidation reactions

“…[9][10][11] The deliberate development of efficient and durable Pd-based AOR electrocatalysts is of great significance for the advances of renewable energy storage and conversion equipment. [12][13][14][15] Pd-based nanoparticles (NPs) tend to migrate and agglomerate during long-term catalysis operation, resulting in a decrease in electrocatalytic stability. [16][17][18] Moreover, incomplete oxidation products such as CO and methyl can readily occupy the Pd active site due to the uncontrollable electronic environment, which can potentially cause catalyst poisoning.…”

“…9–11 The deliberate development of efficient and durable Pd-based AOR electrocatalysts is of great significance for the advances of renewable energy storage and conversion equipment. 12–15…”

Ni2+ Tailoring Pd Enables Nanonet-Structured Catalysts with Dual Doping of H and Ni for Enhanced Alcohol Oxidation

“…with small atomic radius can usually penetrate into the interstitial positions of the lattice structure, profoundly affecting the physical and chemical properties of the host metal, such as lattice parameters, electron transfer properties, and thermal stability . Besides, the strong hybridization between the s–p orbitals of nonmetallic atoms and the d orbitals of noble metals can modulate the electronic structure of surface active sites. , In palladium-nonmetal alloys, palladium hydride (PdH x ) is the most extensively studied catalyst due to the high affinity between Pd and H atoms, which shows excellent performance in various catalytic reactions such as ethanol oxidation, , methanol oxidation, and formate oxidation. , However, the production of PdH x often involves toxic reagents, and the escape of H atoms results in the instability of its structure. The strong adsorption of intermediates can still lead to poisoning of the active center of the PdH x catalysts, causing the rapid decline of catalytic performance over a short period.…”