Ligand-capped pristine and doped ZnO2 nanoparticles for enhanced photocatalytic methylene blue degradation: A DFT-supported study

IF 5.1 2区材料科学 Q1 MATERIALS SCIENCE, CERAMICS

Ceramics International Pub Date : 2025-05-01 DOI:10.1016/j.ceramint.2025.01.482

Imran Ullah , Reinhard B. Neder , Muhammad Irfan Khan , Inam Ud Din , Huma Parwaz , Suriati Sufian

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引用次数: 0

Abstract

In the present work, ligand-assisted zinc peroxide (ZnO₂) nanoparticles (NPs) and doped ZnO₂ NPs (manganese (Mn) and cobalt (Co)) were synthesized via the co-precipitation method and characterized through complementary techniques. Organic ligands, including citrate (cit), 1,5-diphenyl-1,3,5-pentanetrione (pent), and dimethyl-L-tartrate (dmlt), were used to stabilize the NPs and tune their bandgap through Mn and Co doping, thereby enhancing the photocatalytic degradation of methylene blue (MB) dye. The XRD data refinement revealed cuboctahedral-shape crystallites/NPs with diameters ranging from 3 to 12.7 nm. Tauc's relation supported an optical bandgap of 2.96 eV upon 3 % Mn incorporation, which is lower than 3.07 eV for pristine ZnO₂ (cit-capped) NPs. In 150 min, cit-capped pristine ZnO₂ NPs degraded 63.34 % of MB dye; this rate increased to 77.94 %, 93 % upon 3 %, 5 % Mn-doping, and 85.13 %, 81.24 % upon 3 %, 5 % Co doping, respectively. A similar trend was observed for dmlt-capped NPs; pristine ZnO₂ NPs degraded 63.72 % of dye and reached to 72.26 %, 74.25 % upon 3 %, 5 % Mn-doping, and 78.56 %, 79.71 % upon 3 %, 5 % Co-doping in 150 min, respectively. Notably, pent-capped ZnO₂ NPs degraded 98.89 % in 90 min. However, the performance was adversely affected by Mn and Co-doping (83.20 %, 97.35 % for 3 %, 5 % Mn-doped and 78.65, 73.68 % for 3 %, 5 % Co-doped). DFT calculations suggest that Mn and Co-incorporation into ZnO₂ lattice improved thermodynamic and mechanical stability as well as chemical reactivity. The kinetics analysis showed that all reactions follow the pseudo-first-order kinetic model with R-squared values ranging from 84.0 to 98.5. This work demonstrates how doping can improve the performance of ligand-assisted ZnO₂ photocatalysts for enhanced dye degradation.

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配体覆盖的原始和掺杂ZnO2纳米颗粒增强光催化亚甲基蓝降解：一项dft支持的研究

本文采用共沉淀法合成了配体辅助氧化锌（ZnO2）纳米粒子（NPs）和掺杂ZnO2纳米粒子（锰（Mn）和钴（Co）），并通过互补技术对其进行了表征。利用柠檬酸盐（cit）、1,5-二苯基-1,3,5-戊三酮（pent）和二甲基- l-酒石酸盐（dmlt）等有机配体，通过Mn和Co掺杂来稳定NPs并调节其带隙，从而增强对亚甲基蓝（MB）染料的光催化降解。XRD数据精化显示出直径为3 ~ 12.7 nm的立方面状晶体/NPs。Tauc关系支持3% Mn掺杂时的光学带隙为2.96 eV，低于原始ZnO2（柠檬酸封顶）NPs的3.07 eV。在150 min内，城市封顶的原始ZnO2 NPs降解了63.34%的MB染料；掺杂3%、5%锰后，这一比例分别为77.94%、93%，掺杂3%、5%钴后，这一比例分别为85.13%、81.24%。dmlt封顶的NPs也有类似的趋势；原始ZnO2 NPs对染料的降解率为63.72%，在掺杂3%、5%锰后降解率分别为72.26%、74.25%，在掺杂3%、5%共掺杂后降解率分别为78.56%、79.71%。值得注意的是，ppcapped ZnO2 NPs在90 min内降解率为98.89%。然而，Mn和共掺杂对性能有不利影响（Mn掺杂3%、5%时为83.20%、97.35%，Mn掺杂3%、5%时为78.65、73.68%）。DFT计算表明，Mn和co掺入ZnO2晶格改善了热力学和机械稳定性以及化学反应性。动力学分析表明，所有反应均符合准一级动力学模型，r平方值在84.0 ~ 98.5之间。这项工作证明了掺杂如何提高配体辅助ZnO2光催化剂的性能，以增强染料降解。

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来源期刊

Ceramics International 工程技术-材料科学：硅酸盐

CiteScore

9.40

自引率

15.40%

发文量

4558

审稿时长

25 days

期刊介绍： Ceramics International covers the science of advanced ceramic materials. The journal encourages contributions that demonstrate how an understanding of the basic chemical and physical phenomena may direct materials design and stimulate ideas for new or improved processing techniques, in order to obtain materials with desired structural features and properties. Ceramics International covers oxide and non-oxide ceramics, functional glasses, glass ceramics, amorphous inorganic non-metallic materials (and their combinations with metal and organic materials), in the form of particulates, dense or porous bodies, thin/thick films and laminated, graded and composite structures. Process related topics such as ceramic-ceramic joints or joining ceramics with dissimilar materials, as well as surface finishing and conditioning are also covered. Besides traditional processing techniques, manufacturing routes of interest include innovative procedures benefiting from externally applied stresses, electromagnetic fields and energetic beams, as well as top-down and self-assembly nanotechnology approaches. In addition, the journal welcomes submissions on bio-inspired and bio-enabled materials designs, experimentally validated multi scale modelling and simulation for materials design, and the use of the most advanced chemical and physical characterization techniques of structure, properties and behaviour. Technologically relevant low-dimensional systems are a particular focus of Ceramics International. These include 0, 1 and 2-D nanomaterials (also covering CNTs, graphene and related materials, and diamond-like carbons), their nanocomposites, as well as nano-hybrids and hierarchical multifunctional nanostructures that might integrate molecular, biological and electronic components.