Ling Tao, Zhang Tong, Ge Binghui, Han Lili, Zheng Lirong, Lin Feng, Xu Zhengrui, Hu Wen-Bin, Du Xi-Wen, Davey Kenneth, Qiao Shi-Zhang
Key Laboratory for Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin, 300072, China.
School of Chemical Engineering, The University of Adelaide, Adelaide, SA, 5005, Australia.
Adv Mater. 2019 Apr;31(16):e1807771. doi: 10.1002/adma.201807771. Epub 2019 Mar 4.
The practical scale-up of renewable energy technologies will require catalysts that are more efficient and durable than present ones. This is, however, a formidable challenge that will demand a new capability to tailor the electronic structure. Here, an original electronic structure tailoring of CoO by Ni and Zn dual doping is reported. This changes it from an inert material into one that is highly active for the hydrogen evolution reaction (HER). Based on combined density functional theory calculations and cutting-edge characterizations, it is shown that dual Ni and Zn doping is responsible for a highly significant increase in HER activity of the host oxide. That is, the Ni dopants cluster around surface oxygen vacancy of the host oxide and provide an ideal electronic surface structure for hydrogen intermediate binding, while the Zn dopants distribute inside the host oxide and modulate the bulk electronic structure to boost electrical conduction. As a result, the dual-doped Ni, Zn CoO nanorods achieve current densities of 10 and 20 mA cm at overpotentials of, respectively, 53 and 79 mV. This outperforms reported state-of-the-art metal oxide, metal oxide/metal, metal sulfide, and metal phosphide catalysts.
可再生能源技术的实际扩大规模将需要比现有催化剂更高效、更耐用的催化剂。然而，这是一项艰巨的挑战，需要具备调整电子结构的新能力。在此，报道了通过镍和锌双掺杂对氧化钴进行独特的电子结构调整。这使其从一种惰性材料转变为对析氢反应（HER）具有高活性的材料。基于密度泛函理论计算和前沿表征相结合的方法，结果表明镍和锌双掺杂是主体氧化物析氢活性显著提高的原因。也就是说，镍掺杂剂聚集在主体氧化物的表面氧空位周围，为氢中间体结合提供了理想的电子表面结构，而锌掺杂剂分布在主体氧化物内部并调节体相电子结构以促进导电。结果，双掺杂的镍、锌氧化钴纳米棒在过电位分别为53和79 mV时实现了10和20 mA cm的电流密度。这优于已报道的最先进的金属氧化物、金属氧化物/金属、金属硫化物和金属磷化物催化剂。
