Reversing the Activity Center in Doped Pd₁₇Se₁₅ to Achieve High Stability Toward the Electrochemical Hydrogen Evolution Reaction

Abstract

The use of hydrogen, being an environmentally cleaner source of energy, may reduce the pressing problem of CO 2 emissions due to the burning of conventional fossil fuels. However, the prolonged production of hydrogen is a major issue and can be solved through designing a stable electrocatalyst. In this work, we have designed a Ni-doped Pd 17 Se 15 catalyst that retains its activity for 20000 electrochemical cycles. The enhanced stability of this electrocatalyst can be attributed to the reversal of the activity center from the Pd to the Se center through Ni substitution. The concept of activating the chalcogen center and deactivating the Pd site is supported through theoretical calculations. This work provides a unique strategy of tuning catalysts toward higher activity and stability.

Structure‐Tailored Non‐Noble Metal‐based Ternary Chalcogenide Nanocrystals for Pt‐like Electrocatalytic Hydrogen Production

“…Tafel slope analyses on NBS_20, NBS_15, and NBS_12.5 nanoparticles provide Tafel slopes of 58, 83, and 95 mV dec −1 , respectively (Figure 3d), which propose that HER is based on Volmer–Heyrovsky mechanism for all the catalysts. The obtained value of Tafel slope is lower than most of the other non‐Pt‐based electrocatalysts such as Ni‐Pd 17 Se 15 (91.5 mV dec −1 ), [36] Ni 5 P 4 ‐Ni 2 P nanosheets (79.1 mV dec −1 ), [37] Cu 3 P (67 mV dec −1 ), [38] NiS x film (62 mV dec −1 ), [39] and NiCoS (61 mV dec −1 ) [40] . A lower charge‐transfer resistance was obtained with increase of irradiation time indicating better charge‐transfer kinetics and higher activity (Figure 3e).…”

Synthesis of Alloyed Pd−Pb Nanowire Networks for Electrocatalytic Ethanol Oxidation with High Stability

“…Since the electronegativity of Pb is higher than that of Pd, the d-band center of the Pd atom will change due to the transfer of electrons from Pd to Pb during the formation of the alloy, which would weaken the adsorption of toxic intermediates on the catalyst surface and thus lead to the enhancement of the activity of electrocatalytic oxidation of ethanol. [59][60][61][62][63] In general, the introduction of lead leads to the change of electronic structure of palladium, which increases the catalytic activity of the alloy. [57] The electrocatalytic activities of PdÀ Pb NNWs were evaluated by electrochemical measurements.…”

Dealloying Induced Manipulative Disruption of Ni2P–SnP Heterostructure Enabling Enhanced Hydrogen Evolution Reaction

“…The crystal structures of Ni 2 P (SG: P 2 m ) and SnP (SG: Fm m ) were used for EXAFS fitting. The EXAFS data were Fourier transformed based on our previous papers. , …”

“…Metal chalcogenides, − carbides, − and nitrides have been known to demonstrate excellent hydrogen evolution performance. Nevertheless, transition-metal-based phosphides (TMPs) have evolved to be an intriguing class for HER because of their attractive electronic structure, ecological safety, and physicochemical properties. , TMPs though mostly do not meet the need of prolonged durability and considerable energy supply because of the harsh reaction conditions.…”