Polyoxometalate precursors for precisely controlled synthesis of bimetallic sulfide heterostructure through nucleation-doping competition
Polyoxometalate precursors for precisely controlled synthesis of bimetallic sulfide heterostructure through nucleation-doping competition
复制标题
通过成核-掺杂竞争精确控制合成双金属硫化物异质结构的多金属氧酸盐前体
DOI：
10.1039/c8nr00925b
复制
发表时间：
2018
期刊：
影响因子：
6.7
通讯作者：
Lan Ya-Qian
中科院分区：
文献类型：
--
作者：
Tang Yu-Jia;Zhang A-Man;Zhu Hong-Jing;Dong Long-Zhang;Wang Xiao-Li;Li Shun-Li;Han Min;Xu Xiang-Xin;Lan Ya-Qian
二硫化钼（MoS2）基双金属硫化物因其独特的结构和性能而受到越来越多的研究关注。本文首次提出了以anderson型多金属氧酸盐（pom）为双金属源，在碳布上生长一系列双金属硫化物（M - mo - s /CC, M = Co, Ni, Fe）的一锅水热合成方法。采用M-Mo-S /CC的理想模型，通过核掺杂竞争机制研究了生长过程。首次证明了M-Mo-S /CC具有一定的双金属硫化物组成，而不是金属掺杂的MoS2结构，因为成核反应在成核掺杂竞争中占主导地位。此外，由于anderson型pom具有固定的双金属比例和精确的结构，可以通过比较不同金属的成核速率来研究M-Mo-S /CC的不同形貌。Co-Mo-S和Ni-Mo-S表现为球状异质结构，内部主要是CoS2或NiS，外部是相互连接的MoS2纳米片，而Fe-Mo-S表现为均匀的纳米片形貌，没有堆叠。作为碱水电解电极，不同组成和形态的M-Mo-S /CC具有不同的活性。其中，在M-Mo-S /CC样品中，Co-Mo-S /CC的析氢反应、析氧反应和整体水裂解性能最好。本研究提出了一种简单的策略，利用聚甲醛作为双金属前驱体来研究mos2基双金属硫化物的生长机理和水电解性能。
Molybdenum disulfide (MoS2)-based bimetallic sulfides have drawn increasing research attention because of their unique structures and properties. Herein, a one-pot hydrothermal synthesis method is proposed to grow a series of bimetallic sulfides on carbon cloth (M–Mo–S/CC, M = Co, Ni, Fe) using Anderson-type polyoxometalates (POMs) as bimetallic sources for the first time. An ideal model of M–Mo–S/CC was used to study the growth process through the nucleation-doping competition mechanism. It is proved for the first time that M–Mo–S/CC possess certain compositions of bimetallic sulfides rather than metal doped MoS2 structures because the nucleation reaction is predominant in the nucleation-doping competition. Moreover, the nucleation rates of different metals can be compared to study the different morphologies of M–Mo–S/CC because Anderson-type POMs have fixed bimetal proportions and precise structures. Co–Mo–S and Ni–Mo–S show spherical heterostructures with CoS2 or NiS mainly inside and interconnected MoS2 nanosheets outside, while Fe–Mo–S exhibits uniform nanosheet morphology without stacking. As electrodes for alkaline water electrolysis, M–Mo–S/CC with different compositions and morphologies exhibit a variety of activities. Particularly, among the M–Mo–S/CC samples, Co–Mo–S/CC achieves the best performance for hydrogen evolution reaction, oxygen evolution reaction and overall water splitting. This study presents a facile strategy of using POMs as bimetallic precursors for studying the growth mechanism as well as the water electrolysis performances of MoS2-based bimetallic sulfides.