六元环状羟基氟化锰的可控合成及水氧化性能

引用本文: 张艳, 陈迎冬, 梁作中, 齐静, 高学庆, 张伟, 曹睿. 六元环状羟基氟化锰的可控合成及水氧化性能[J]. 催化学报, 2019, 40(12): 1860-1866. doi: S1872-2067(19)63306-1 shu

Citation: Yan Zhang, Yingdong Chen, Zuozhong Liang, Jing Qi, Xueqing Gao, Wei Zhang, Rui Cao. Controlled synthesis of hexagonal annular Mn(OH)F for water oxidation[J]. Chinese Journal of Catalysis, 2019, 40(12): 1860-1866. doi: S1872-2067(19)63306-1 shu

六元环状羟基氟化锰的可控合成及水氧化性能

张艳 ^a, ,
陈迎冬 ^a, ,
梁作中 ^a, ,
齐静 ^a, ,
高学庆 ^a, ,
张伟 ^a, ,
曹睿 ^a,b,

a 陕西师范大学化学化工学院应用表面与胶体化学教育部重点实验室, 陕西西安 710119;
b 中国人民大学化学系, 北京 100872
基金项目:
中国千人计划；陕西师范大学科研启动基金；国家自然科学基金（21503126，21573139，21773146，21872092）.

摘要: 含特殊结构的材料，尤其具有内腔的环状材料，因其独特的物理和化学性质而引起了人们的极大兴趣.目前已经合成了许多环状材料，广泛应用于催化，传感，生物医学，环境保护，储能等领域.然而，这些环状材料的合成方法大多比较复杂和困难.如早期的模板技术，以及用微波辅助法和湿化学法合成α-Fe₂O₃，Sb₂Te₃纳米线，ZnO和Ni（OH）₂/Co（OH）₂空心纳米六元环等.因此，通过简单的方法来合成形貌均匀的环状结构材料仍然是一个巨大的挑战.近期的研究表明，金属氢氧化物，氟化物以及羟基氟化物被广泛应用于水氧化和储能等领域.本文通过简单的水热法合成了一种新型的六元环状的羟基氟化锰，它具有良好的水氧化催化性能.
粉末X射线衍射结果显示，当水合肼用量为4mmol时，在不添加氟化铵的条件下得到的样品是Mn₃O₄；随着氟化铵用量增加到4mmol时为羟基氟化锰，并得到红外、热重分析、能谱、X射线光电子能谱等表征的证实.为了探究六元环状的羟基氟化锰的生长过程，我们控制水热反应的温度和时间，通过扫描电子显微镜表征了样品在不同的温度和时间条件下的形貌.发现在较低的温度和较短的反应时间下得到的是表面粗糙的六角形的块状材料；随着温度和反应时间的增加，氟化铵和水合肼分解，氟离子在材料的表面不断刻蚀，形成了核壳结构的形貌；当于160℃反应6h时形成了环状的羟基氟化锰.随后通过理论模型解释了这种环状材料的生长机理.为了探究结构和性能之间的关系，在1mol/L KOH溶液中对160℃反应1h得到的六元块状形貌的氟化羟基锰和反应6h得到的六元环状氟化羟基锰的电催化水氧化性能进行了研究.结果表明，环状的氟化羟基锰的起峰电位是1.53V，块状的为1.58V，可见前者具有较低的起峰电位，更高的电流密度.塔菲尔测试结果显示了环状的塔菲尔斜率（184mV/dec）比块状（293mV/dec）的小，表明环状材料的质量扩散的效率相对较高.这可能由于环状结构的材料暴露了内腔，暴露出更多的水氧化活性位点.

关键词:

English

Controlled synthesis of hexagonal annular Mn(OH)F for water oxidation

a Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, Shaanxi, China;
b Department of Chemistry, Renmin University of China, Beijing 100872, China
Received Date: 31 January 2019
Revised Date: 16 February 2019
Fund Project:
This work was supported by the "Thousand Talents Program" of China, the Starting Research Funds of Shaanxi Normal University, and the National Natural Science Foundation of China (21503126, 21573139, 21773146, 21872092).

Abstract: Controlling the morphology and size of materials is very important for their chemical and physical properties. Herein, we synthesized a novel hexagonal annular Mn(OH)F by a simple hydrothermal method. We also investigated the growth process of the materials from hexagonal block to hexagonal ring via controlling the hydrothermal temperature and time. Comparing with the hexagonal block, the hexagonal rings showed enhanced electrocatalytic water oxidation performance in alkaline solutions. The observed catalytic performance of this novel Mn(OH)F is correlated to its unique structure. Furthermore, we expect that Mn(OH)F would be a new type of Mn-based water oxidation catalyst.

Key words:

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六元环状羟基氟化锰的可控合成及水氧化性能

English

Controlled synthesis of hexagonal annular Mn(OH)F for water oxidation

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

六元环状羟基氟化锰的可控合成及水氧化性能

English

Controlled synthesis of hexagonal annular Mn(OH)F for water oxidation

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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