Growth of graphene-supported hollow cobalt sulfide nanocrystals via MOF-templated ligand exchange as surface-bound radical sinks for highly efficient bisphenol A degradation
Growth of graphene-supported hollow cobalt sulfide nanocrystals via MOF-templated ligand exchange as surface-bound radical sinks for highly efficient bisphenol A degradation
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通过 MOF 模板配体交换作为表面结合自由基汇生长石墨烯支撑的空心硫化钴纳米晶体，实现高效双酚 A 降解
DOI：
10.1016/j.apcatb.2018.09.088
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发表时间：
2019-03
期刊：
影响因子：
--
通讯作者：
Li Aimin
中科院分区：
文献类型：
--
作者：
Zhu Changqing;Liu Fuqiang;Ling Chen;Jiang Hao;Wu Haide;Li Aimin
以金属有机骨架（MOFs）为模板，通过简单的配体交换法制备了石墨烯纳米片负载的硫化钴空心纳米晶（Co3S4@GN，CoS@GN）.随后的热退火诱导了Co3S4向CoS的相变。这种合成策略驱使咪唑骨架（ZIF-67）内的钴离子向外迁移，形成由大量暴露的活性位点组成的高反应性壳层，以活化基于硫酸根（SO4 radical dot −）的高级氧化过程（SR-AOP）中的过一硫酸根（PMS）。石墨烯载体在富集目标污染物以及吸附分子和自由基之间的电荷转移方面表现出优异的效率。对所制备的纳米催化剂进行了表征，并将其应用于双酚A（BPA）的催化降解。得益于其独特的结构特征，该纳米复合材料在较宽的pH范围内表现出上级催化活性。在8min内，催化剂对BPA的降解率可达100%，动力学常数（0.62min-1）比文献报道的多相催化剂高1-2个数量级。此外，石墨烯载体在调节自由基的种类和作用位点方面的关键作用首次得到解决。石墨烯的吸附性和导电性使得SO4自由基dot-一经产生即被消耗，限制了SO4自由基dot-向催化剂表面的扩散和自由基dotOH的生成。该催化剂作为一个表面结合的SO4自由基的点-汇吸附BPA的原位降解。催化剂表征和密度泛函理论（DFT）计算证实了CoS@GN在以Co（II）为活性中心生成SO4自由基dot −方面的优异活性。为避免催化剂损失，构建了CoS@GN涂层膜反应器，连续3个循环运行良好，表明催化剂可重复使用，系统稳定性良好。总之，这项工作为MOFs在环境中的应用开辟了一条新的道路，并提供了一种新的钴基纳米催化剂家族，以产生表面结合的自由基，用于SR-AOP降解柠檬酸盐污染物。
Graphene nanosheet-supported hollow cobalt sulfide nanocrystals (Co3S4@GN, CoS@GN) were fabricated via a facile ligand exchange route using metal-organic frameworks (MOFs) as self-templates. Subsequent thermal annealing induced the phase transformation of Co3S4to CoS. This synthesis strategy drove the cobalt ions inside zeolitic imidazolate frameworks (ZIF-67) to migrate outwards, forming a highly reactive shell composed of abundant exposed active sites to activate peroxymonosulfate (PMS) in the sulfate radical (SO4radical dot−)-based advanced oxidation process (SR-AOP). The graphene support exhibited excellent efficiencies in the enrichment of targeted pollutant as well as the charge transfer between absorbed molecules and radicals. The nanocatalysts were fully characterized and applied to the catalytic degradation of bisphenol A (BPA). Benefitting from the unique structure characteristic, the as-synthesized nanocomposites showed superior catalytic activities over a broad pH range. The degradation efficiency of BPA reached ∼100% within 8 min by using CoS@GN, and the kinetic constant (0.62 min-1) was higher than those of most reported heterogeneous catalysts by 1–2 orders of magnitude. Furthermore, the critical roles of graphene support in regulating the variety and action site of radicals were addressed for the first time. The adsorptive and conductive graphene made the SO4radical dot−once produced was consumed immediately, which limited the diffusion of SO4radical dot−out of catalyst surface and the generation ofradical dotOH. The catalyst served as a surface-bound SO4radical dot−sink for the in-situ degradation of adsorbed BPA. Catalyst characterizations and the Density-Functional-Theory (DFT) calculation confirmed the excellent activity of CoS@GN in yielding SO4radical dot−with Co(II) as the active center. A CoS@GN-coated membrane reactor was constructed to avoid catalyst loss and worked well in consecutive 3 cycles, suggesting the satisfactory catalyst reusability and system robustness. Overall, this work paved a new way for MOFs in the environmental application and provided a novel family of Co-based nanocatalysts to produce surface-bound radicals for recalcitrant contaminant degradation by SR-AOP.
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