RESUMO
Pd-based electrocatalysts are the most effective catalysts for ethylene glycol oxidation reaction (EGOR), while the disadvantages of poor stability, low resistance to neutrophilic, and low catalytic activity seriously hamper the development of direct ethylene glycol fuel cells (DEGFCs). In this work, defect-riched PdCoZn nanosheets (D-PdCoZn NSs) with ultrathin 2D NSs and porous structures are fabricated through the solvothermal and alkali etching processes. Benefiting from the presence of defects and ultrathin 2D structures, D-PdCoZn NSs demonstrate excellent electrocatalytic activity and good durability against EGOR in alkaline media. The mass activity and specific activity of D-PdCoZn NSs for EGOR are 9.5 A mg-1 and 15.7 mA cm-2 , respectively, which are higher than that of PdCoZn NSs, PdCo NSs, and Pd black. The D-PdCoZn NSs still maintain satisfactory mass activity after long-term durability tests. Meanwhile, in situ IR spectroscopy demonstrates that the presence of defects attenuated the adsorption of intermediates, which improves the selectivity of the C1 pathway with excellent anti-CO poisoning performance. This work not only provides an effective synthetic strategy for the preparation of Pd-based nanomaterials with defective structures but also indicates significant guidance for optimum C1 pathway selectivity of ethylene glycol and other challenging chemical transformations.
RESUMO
Efficient and low-cost electrocatalysts for the hydrogen evolution reaction (HER) are required for producing hydrogen energy through water splitting. Carbon materials as HER catalyst supports are explored widely since the strong metal-support interactions are generally believed to be active and stable toward HER. Herein, we report N-doped porous carbon materials as novel substrates to stabilize the cluster metal sites through the Ru(III) polyamine complexes, which play an important role not only in efficient electron transfer but also in the increasing utilization of metallic active sites. Meanwhile, due to the strong metal-support interactions driven by Ru(III) polyamine complexes, the obtained Ru cluster with a mass loading of 3% on N-doped porous carbon nanoplates (Ru cluster@NCs) exhibits robust stability for HER at a constant voltage, proving to be a promising candidate catalyst for HER. Density functional theory calculations further indicate that the Gibbs free energy (ΔG) of adsorbed H* of Ru cluster@NCs is much closer to zero compared to Ru@(10%)NCs and Pt/C(20%), thus Ru cluster@NCs facilitate the HER process.
RESUMO
Design high-loading with superior activity and high atomic efficiency has consistently been a new frontier of heterogeneous catalysis while challenging in synthetic technology. In this work, a universal solid-state strategy is proposed for large scalable production of high-loading Ir clusters on porous hollow carbon nanobowls (Ir CSs/PHCNBs). The strong electronic interaction between metallic Ir cluster and C on PHCNBs leads to electron redistribution, which significantly improves the electron transfer rate on the interface. The obtained Ir CSs/PHCNBs only require overpotentials of 35, 34, and 37 mV for the hydrogen evolution reaction (HER) with stable outputting of 10 mA cm-2 under acidic, alkaline, and neutral conditions, respectively, which exceeds the state-of-the-art HER electrocatalysts. Meanwhile, the Tafel slopes of Ir CSs/PHCNBs for the HER process are 23.07, 48.76, and 28.95 mV dec-1 , greatly lower than that of PHCNBs (152.73, 227.96, and 140.29 mV dec-1 ) and commercial Pt/C (20%) (36.33, 66.10, and 36.61 mV dec-1 ). These results provide a new strategy for the universal synthesis of clusters catalysts and insight into understanding the interface effects between clusters and carbon substrate, facilitating the industrial application of hydrogen production.
