A Low-Temperature Synthetic Route Toward a High-Entropy 2D Hexernary Transition Metal Dichalcogenide for Hydrogen Evolution Electrocatalysis.
A Low-Temperature Synthetic Route Toward a High-Entropy 2D Hexernary Transition Metal Dichalcogenide for Hydrogen Evolution Electrocatalysis.
复制标题
低温合成途径，通向高渗透2D六六角型过渡金属二甲基化元素，用于氢进化电催化。
DOI：
10.1002/advs.202204488
复制
发表时间：
2023-05
期刊：
影响因子：
15.1
通讯作者：
Lewis, David J.
中科院分区：
文献类型：
--
作者：
Qu, Jie;Elgendy, Amr;Cai, Rongsheng;Buckingham, Mark A.;Papaderakis, Athanasios A.;de Latour, Hugo;Hazeldine, Kerry;Whitehead, George F. S.;Alam, Firoz;Smith, Charles T.;Binks, David J.;Walton, Alex;Skelton, Jonathan M.;Dryfe, Robert A. W.;Haigh, Sarah J.;Lewis, David J.
关键词：
高熵金属硫化物是一类在热电、电催化等领域具有巨大应用潜力的材料。层状2D过渡金属二卤化物(TMDCs)是高熵金属硫化物的一个子类，由于目前其制备涉及复杂、能源密集型或危险的合成步骤，迄今很少受到关注。针对这一问题，采用低温(500℃)、快速(1h)的单源前驱体方法成功地合成了六元系高熵金属二硫化物(MoWReMnCr)S2。用粉末X射线衍射仪和拉曼光谱对(MoWReMnCr)S2粉末进行了表征，证实了该材料主要由六方相组成。用X射线光电子能谱(XPS)研究了表面氧化态和元素组成，用扫描电子显微镜(SEM)结合能谱(EDX)获得的元素图谱信息确定了块体形貌和元素化学计量比的空间分布。随后，通过液相剥离(LPE)将块状分层材料剥离成超薄的、多层的2D纳米薄片。用高角度环形暗场扫描透射电子显微镜(HAADF-STEM)和EDX图谱发现，所得到的几层HE(MoWReMnCr)S2纳米片在纳米尺度上包含均匀的金属元素分布。最后证明了(MoWReMnCr)S2是一种析氢电催化剂，并与分子前驱体法制备的2H-MoS2进行了比较。在0.5M的H_2SO_4中，(MoWReMnCr)S_2的过电位为229 mV，电流密度为10 mA cm−_2，远低于MoS_2的过电位362 mV。根据密度泛函理论计算，假设催化活性的提高是由于在2H-MoS_2结构中加入其他元素，特别是第一排TMS的铬和锰时基面的活化。以5个独立的分子前驱体为原料，在500℃的较低温度下热分解1h，合成了一种新型的高熵硫化物(MoWReMnCr)S2，测试了由这些高熵层状材料制备的剥离的2D纳米片在氢析出反应(HER)中的电催化活性，并与广泛研究的电催化剂2H-MoS2进行了比较。
High‐entropy (HE) metal chalcogenides are a class of materials that have great potential in applications such as thermoelectrics and electrocatalysis. Layered 2D transition‐metal dichalcogenides (TMDCs) are a sub‐class of high entropy metal chalcogenides that have received little attention to date as their preparation currently involves complicated, energy‐intensive, or hazardous synthetic steps. To address this, a low‐temperature (500 °C) and rapid (1 h) single source precursor approach is successfully adopted to synthesize the hexernary high‐entropy metal disulfide (MoWReMnCr)S2. (MoWReMnCr)S2 powders are characterized by powder X‐ray diffraction (pXRD) and Raman spectroscopy, which confirmed that the material is comprised predominantly of a hexagonal phase. The surface oxidation states and elemental compositions are studied by X‐ray photoelectron spectroscopy (XPS) whilst the bulk morphology and elemental stoichiometry with spatial distribution is determined by scanning electron microscopy (SEM) with elemental mapping information acquired from energy‐dispersive X‐ray (EDX) spectroscopy. The bulk, layered material is subsequently exfoliated to ultra‐thin, several‐layer 2D nanosheets by liquid‐phase exfoliation (LPE). The resulting few‐layer HE (MoWReMnCr)S2 nanosheets are found to contain a homogeneous elemental distribution of metals at the nanoscale by high angle annular dark field‐scanning transmission electron microscopy (HAADF‐STEM) with EDX mapping. Finally, (MoWReMnCr)S2 is demonstrated as a hydrogen evolution electrocatalyst and compared to 2H‐MoS2 synthesized using the molecular precursor approach. (MoWReMnCr)S2 with 20% w/w of high‐conductivity carbon black displays a low overpotential of 229 mV in 0.5 M H2SO4 to reach a current density of 10 mA cm−2, which is much lower than the overpotential of 362 mV for MoS2. From density functional theory calculations, it is hypothesised that the enhanced catalytic activity is due to activation of the basal plane upon incorporation of other elements into the 2H‐MoS2 structure, in particular, the first row TMs Cr and Mn. A novel high entropy sulfide (MoWReMnCr)S2 is synthesized by facile thermal decomposition of a cocktail of five individual molecular precursors at a relatively low temperature of 500 °C for 1 h. The performance of the exfoliated 2D nanosheets derived from these high entropy layered materials are measured for electrocatalytic activity in the hydrogen evolution reaction (HER) and the results compared to the widely‐studied electrocatalyst 2H‐MoS2.
登录
查看更多内容
影响因子：
10.8
作者：
Gong, Yongji;Liu, Zheng;Ajayan, Pulickel M.
通讯作者：
Ajayan, Pulickel M.
影响因子：
6.4
作者：
Alqahtani, Tahani;Cernik, Robert J.;Lewis, David J.
通讯作者：
Lewis, David J.
影响因子：
56.9
作者：
Jaramillo, Thomas F.;Jorgensen, Kristina P.;Chorkendorff, Ib
通讯作者：
Chorkendorff, Ib
原子薄过渡金属二硫属化物合金的可调谐带隙光致发光
影响因子：
17.1
作者：
Chen, Yanfeng;Xi, Jinyang;Xie, Liming
通讯作者：
Xie, Liming
影响因子：
17.1
作者：
Lee, Changgu;Yan, Hugen;Ryu, Sunmin
通讯作者：
Ryu, Sunmin