Mn-Doping-Induced Co3O4 Structural Distortion and Facet Change for Enhanced Electro-Activation of O2 toward Pollutants Removal

IF 7.4 Q1 ENGINEERING, ENVIRONMENTAL ACS ES&T engineering Pub Date : 2024-06-03 DOI:10.1021/acsestengg.4c00165

Min Sun, Sheng-Nan Tang, Zi-Xu Chen, Lin-Feng Zhai, Yuanhua Xia, Shaobin Wang

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Abstract

Oxygen is a green oxidant for the oxidative removal of environmental pollutants. In this work, we employed Mn-doped Co₃O₄ for electrocatalytic activation of O₂ and investigated the effects of structure and facet on catalysis. Co³⁺ substitution by Mn³⁺/Mn⁴⁺ leads to Co₃O₄ structural distortion and a shift of preferentially exposed (311) to a more catalytically active (220) plane. Meanwhile, more vacancies are created due to the structural defects and charge imbalance between Co³⁺ and Mn⁴⁺. Experimental and theoretical investigations suggest that Mn-doping facilitates adsorption of O₂ on the deficient (220) plane of Co₃O₄ by triggering a thermodynamically more stable Mn_0.65Co_2.35O₄-[O₂]* intermediate. Mn_0.65Co_2.35O₄ gives a turnover frequency value 9.5 times higher than that for pure Co₃O₄. The electrocatalytic wet air oxidation process with Mn_0.65Co_2.35O₄ shows a great energy-saving merit with specific energy consumptions as low as 2.2–5.0 kW h kg-TOC^–1 in mineralizing phenolic compounds. This work opens up new opportunities for advancing air oxidation technology into more competitive processes.

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掺锰诱导的 Co3O4 结构畸变和刻面变化可增强氧气的电活化能力，从而去除污染物

氧气是氧化去除环境污染物的绿色氧化剂。在这项工作中，我们采用掺杂 Mn 的 Co3O4 对 O2 进行电催化活化，并研究了结构和刻面对催化作用的影响。Mn3+/Mn4+取代Co3+会导致Co3O4结构畸变，并将优先暴露的（311）面转移到催化活性更高的（220）面。同时，由于结构缺陷以及 Co3+ 和 Mn4+ 之间的电荷不平衡，产生了更多的空位。实验和理论研究表明，掺杂锰可引发热力学上更稳定的 Mn0.65Co2.35O4-[O2]* 中间体，从而促进 O2 在 Co3O4 的缺陷（220）面上的吸附。Mn0.65Co2.35O4 的翻转频率值是纯 Co3O4 的 9.5 倍。使用 Mn0.65Co2.35O4 的电催化湿空气氧化工艺在矿化酚类化合物方面显示出巨大的节能优势，比能耗低至 2.2-5.0 kW h kg-TOC-1。这项工作为将空气氧化技术提升为更具竞争力的工艺提供了新的机遇。

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来源期刊

ACS ES&T engineering ENGINEERING, ENVIRONMENTAL-

CiteScore

8.50

自引率

0.00%

发文量

期刊介绍： ACS ES&T Engineering publishes impactful research and review articles across all realms of environmental technology and engineering, employing a rigorous peer-review process. As a specialized journal, it aims to provide an international platform for research and innovation, inviting contributions on materials technologies, processes, data analytics, and engineering systems that can effectively manage, protect, and remediate air, water, and soil quality, as well as treat wastes and recover resources. The journal encourages research that supports informed decision-making within complex engineered systems and is grounded in mechanistic science and analytics, describing intricate environmental engineering systems. It considers papers presenting novel advancements, spanning from laboratory discovery to field-based application. However, case or demonstration studies lacking significant scientific advancements and technological innovations are not within its scope. Contributions containing experimental and/or theoretical methods, rooted in engineering principles and integrated with knowledge from other disciplines, are welcomed.