Key Laboratory of Applied Surface and Colloid Chemistry (MOE), Shaanxi Key Laboratory for Advanced Energy Devices, Shaanxi Engineering Lab for Advanced Energy Technology, School of Materials Science and Engineering , Shaanxi Normal University , Xi'an 710062 , P. R. China.
ACS Appl Mater Interfaces. 2019 Sep 25;11(38):35039-35049. doi: 10.1021/acsami.9b13586. Epub 2019 Sep 10.
The development of highly effective and low-cost electrocatalysts for energy-saving hydrogen production via water splitting is still a great challenge. Herein, porous nitrogen-doped carbon nanobowls (N-CBs) have been designed and used for the controlled growth of ultrafine rhodium (Rh) nanoparticles. With the aid of interfacial bonding of Rh and N, ultrafine Rh nanoparticles with an average size of 1.4 nm have been successfully immobilized on the N-CBs. This Rh/N-CB electrocatalyst shows superior activity and high stability for the hydrogen evolution reaction (HER) and the hydrazine oxidation reaction (HzOR). More importantly, the Rh/N-CBs exhibit high activity for hydrogen production from water electrolysis, marking with a cell voltage of 0.2 V to achieve a current density of 20 mA cm when they serve as cathodic electrocatalysts for the HER and anodic electrocatalysts for the HzOR in 1 M KOH with 0.5 M hydrazine. The density functional theory calculations demonstrate that a near-zero hydrogen adsorption free energy produced by the chemical bonding of Rh with the pyrrole-N doped in N-CBs is responsible for the excellent HER activity of Rh/N-CBs electrocatalysts.
通过水分解来节能制氢的高效且低成本电催化剂的开发仍然是一个巨大的挑战。在此,设计并使用了多孔氮掺杂碳纳米碗(N-CBs)来控制超细微的铑(Rh)纳米颗粒的生长。在 Rh 和 N 的界面键合的作用下,成功地将平均粒径为 1.4nm 的超细微 Rh 纳米颗粒固定在 N-CBs 上。这种 Rh/N-CB 电催化剂在析氢反应(HER)和联氨氧化反应(HzOR)中表现出优异的活性和高稳定性。更重要的是,Rh/N-CBs 作为 HER 的阴极电催化剂和 HzOR 的阳极电催化剂,在 1 M KOH 中含有 0.5 M 联氨时,其析水电解产氢的性能很高,当电池电压为 0.2V 时,电流密度可达 20 mA cm。密度泛函理论计算表明,由 Rh 与 N-CBs 中吡咯-N 掺杂形成的化学键产生的近乎为零的氢吸附自由能是 Rh/N-CB 电催化剂具有优异 HER 活性的原因。