TY - JOUR
T1 - A newly-explored Pd-based nanocrystal for the pH-universal electrosynthesis of H2O2
AU - Yang, Chengyong
AU - Bai, Shuxing
AU - Yu, Zhiyong
AU - Feng, Yonggang
AU - Huang, Bolong
AU - Lu, Qiuyang
AU - Wu, Tong
AU - Sun, Mingzi
AU - Zhu, Ting
AU - Cheng, Chen
AU - Zhang, Liang
AU - Shao, Qi
AU - Huang, Xiaoqing
N1 - Funding Information:
The authors gratefully acknowledge the support of the Natural Science Foundation of China (Grant No.: NSFC 21771156 ).
Publisher Copyright:
© 2021 The Authors
PY - 2021/11
Y1 - 2021/11
N2 - For the generation of hydrogen peroxide (H2O2), a robust electrocatalyst with high activity, selectivity and stability under pH-universal conditions is a formidable challenge. Herein, Pd4Se nanoparticles (NPs) have been proposed as a highly active, selective and durable electrocatalyst for H2O2 production over a wide pH range for the first time. In particular, the Pd4Se NPs show superior H2O2 production selectivities of 93.5%, 89.7%, and 86.7% in 0.1 M HClO4, 0.1 M KCl and 0.1 M KOH electrolytes, respectively. Density functional theory (DFT) calculations reveal that Se incorporation prevents the O[dbnd]O early-cleavage issue by suppressing the excessive electronegativity of the Pd sites. In addition, a strong p-d repulsive correlation shifts the Pd-4d band towards the electron-depleting centre, allowing near-barrier-free electron transfer and facilitating [OOH-] stabilization. Owing to a high energy barrier of the dissociation of [OOH-], the four-electrons oxygen reduction pathway is significantly suppressed for high H2O2 selectivity. The Pd4Se NPs are also highly stable, with only a 2.4%, 9.6% and 3.4% decrease for H2O2 selectivity in 0.1 M HClO4, 0.1 M KCl and 0.1 M KOH electrolytes, respectively, after 5000 cycles, which shows that these NPs are a unique and robust Pd-based electrocatalyst for H2O2 generation under pH-universal conditions.
AB - For the generation of hydrogen peroxide (H2O2), a robust electrocatalyst with high activity, selectivity and stability under pH-universal conditions is a formidable challenge. Herein, Pd4Se nanoparticles (NPs) have been proposed as a highly active, selective and durable electrocatalyst for H2O2 production over a wide pH range for the first time. In particular, the Pd4Se NPs show superior H2O2 production selectivities of 93.5%, 89.7%, and 86.7% in 0.1 M HClO4, 0.1 M KCl and 0.1 M KOH electrolytes, respectively. Density functional theory (DFT) calculations reveal that Se incorporation prevents the O[dbnd]O early-cleavage issue by suppressing the excessive electronegativity of the Pd sites. In addition, a strong p-d repulsive correlation shifts the Pd-4d band towards the electron-depleting centre, allowing near-barrier-free electron transfer and facilitating [OOH-] stabilization. Owing to a high energy barrier of the dissociation of [OOH-], the four-electrons oxygen reduction pathway is significantly suppressed for high H2O2 selectivity. The Pd4Se NPs are also highly stable, with only a 2.4%, 9.6% and 3.4% decrease for H2O2 selectivity in 0.1 M HClO4, 0.1 M KCl and 0.1 M KOH electrolytes, respectively, after 5000 cycles, which shows that these NPs are a unique and robust Pd-based electrocatalyst for H2O2 generation under pH-universal conditions.
KW - HO electrosynthesis
KW - High selectivity
KW - P-d coupling
KW - PH-universal
KW - SePd alloy
UR - http://www.scopus.com/inward/record.url?scp=85114141173&partnerID=8YFLogxK
U2 - 10.1016/j.nanoen.2021.106480
DO - 10.1016/j.nanoen.2021.106480
M3 - Journal article
AN - SCOPUS:85114141173
SN - 2211-2855
VL - 89
JO - Nano Energy
JF - Nano Energy
M1 - 106480
ER -