†Hefei National Laboratory for Physical Sciences at the Microscale, Collaborative Innovation Center of Chemistry for Energy Materials, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
‡CAS Key Laboratory of Materials for Energy Conversion and Department of Material Science and Engineering, University of Science and Technology of China, Hefei, Anhui 230026, PR China.
J Am Chem Soc. 2015 Apr 1;137(12):4119-25. doi: 10.1021/ja5119495. Epub 2015 Mar 17.
Exploring efficient and inexpensive oxygen evolution reaction (OER) electrocatalysts is of great importance for various electrochemical energy storage and conversion technologies. Ni-based electrocatalysts have been actively pursued because of their promising activity and earth abundance. However, the OER efficiency for most of the developed Ni-based electrocatalysts has been intrinsically limited due to their low electrical conductivity and poor active site exposure yield. Herein, we report metallic Ni3N nanosheets as an efficient OER electrocatalyst for the first time. The first-principles calculations and electrical transport property measurements unravel that the Ni3N is intrinsically metallic, and the carrier concentration can be remarkably improved with dimensional confinement. The EXAFS spectra provide solid evidence that the Ni3N nanosheets have disordered structure resultant of dimensional reduction, which then could provide more active sites for OER. Benefiting from enhanced electrical conductivity with metallic behavior and atomically disordered structure, the Ni3N nanosheets realize intrinsically improved OER activity compared with bulk Ni3N and NiO nanosheets. Our finding suggests that metallic nitride nanosheets could serve as a new group of OER electrocatalysts with excellent property.
探索高效且廉价的析氧反应(OER)电催化剂对于各种电化学储能和转化技术至关重要。由于具有较高的活性和丰富的储量,镍基电催化剂受到了广泛关注。然而,由于电导率低和活性位点暴露率差,大多数开发的镍基电催化剂的 OER 效率受到了内在限制。在此,我们首次报道了金属态 Ni3N 纳米片作为高效 OER 电催化剂。第一性原理计算和输运性质测量表明 Ni3N 本质上是金属的,并且尺寸限制可以显著提高载流子浓度。EXAFS 谱提供了确凿的证据,表明 Ni3N 纳米片具有由于尺寸减小而产生的无序结构,这为 OER 提供了更多的活性位点。得益于金属特性和原子无序结构增强的导电性,与体相 Ni3N 和 NiO 纳米片相比,Ni3N 纳米片表现出内在改善的 OER 活性。我们的发现表明,金属氮化物纳米片可以作为一类具有优异性能的新型 OER 电催化剂。