Biodiversity Benefits for Size Modulation of Metal Nanoparticles to Achieve In Situ Semi‐Oxidation toward Optimized Electrocatalytic Oxygen Evolution

Abstract

Biodiversity endows similar species with subtle differences in composition, microstructure, and surface chemistry, making biomass a promising precursor to control the resulting active structure for heterocatalysis. Here, it is shown that Tremella fuciformis (Tfu), possessing an abundant porous structure and favorable metal affinity, is favorably serves as a precursor for confining uniform metal nanoparticles, by comparing the chemical characteristics of six varieties of agarics. The modest size of Co in the Tfu derived composite, Co@NPC‐Tfu (NPC = N, P co‐doped carbon), is suitable for in situ semi‐oxidation during oxygen evolution reaction (OER), forming a stable core‐shell structure of Co3O4@Co. Thus, Co@NPC‐Tfu can be used as a state‐of‐the‐art electrocatalyst for OER with an overpotential of 213.6 ± 4.1 mV at 10 mA cm−2, and a significant turnover frequency of 3.21 s−1 at 300 mV, benefitting from the optimum trade‐off between the atom utilization and electrical conductivity. Operando spectroscopy and theoretical calculations unveil the occupied state modulation of the robust carbon‐bonded POx groups, which optimizes the intermediate adsorption to accelerate OER kinetics. Moreover, Tfu derived Ni@NPC‐Tfu can be also prepared as a high‐performance hydrogen evolution reaction electrocatalyst, which can be utilized for efficient overall water splitting coupled with Co@NPC‐Tfu.

Biomass‐Derived Carbon‐Based Multicomponent Integration Catalysts for Electrochemical Water Splitting

“…Operando spectroscopy combined with theoretical calculations disclosed that the carbon-bonded PO x groups, which are in-situ generated during annealing, can accelerate the OER kinetic of cobalt oxides through modulating the metal occupied states (MOS) (Figure 10 D). [142] This work proves that biodiversity can effectively modulate the chemical properties of metal nanoparticles and carbon supports in biomass-derived composites, and offers a new perspective for the controllable synthesis of biomass-derived catalytic materials. It is worth mentioning that the preparation process of most biomass-derived electrocatalysts requires high temperature pyrolysis, which leads to the serious consideration of energy consumption and environmental protection (generation of tail gas during pyrolysis) in large-scale applications.…”

Optimizing the Spatial Density of Single Co Sites via Molecular Spacing for Facilitating Sustainable Water Oxidation

“…Besides, CoPc-PM@CNT worked even better at HCD since the ratio of Δη/Δlog| j | for CoPc-PM@CNT was remarkably lower than that of IrO 2 at HCD (Figure S38). , Considering the substrate effect, we further evaluated the OER performance of CoPc-PM@CNT on other conductive substrates, such as Au foam, Co foam, and Ni foam (Figures S39 and S40). Under industrial conditions, the overpotential at 2.0 A·cm geo –2 was 307.5 ± 4.4 mV on Au foam and 319.4 ± 3.2 mV on Co foam, being smaller than those on Ni foam (391.2 ± 5.3) and CC (Figures e and S41).…”