The ligand effect of graphene quantum dots in NiFeOx/FeNi3 heterostructure for enhanced electrocatalytic valorization of poly(ethylene terephthalate) plastics

IF 14.9 1区 化学 Q1 Energy
Bo Peng, Sheng Qian, Shuhui Ma, Yi Zhang, Huaiguo Xue, Tengfei Jiang, Jingqi Tian
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Abstract

Electrocatalytic valorization of disused poly (ethylene terephthalate) (PET) plastics into value-added chemicals emerges as a potential approach to address plastic pollution and resources upgrading, but it faces challenges in the development of efficient catalysts for PET-derived ethylene glycol (EG) electrooxidation. Herein, we proposed pyramid arrays on sheet Fe-doped NiO/FeNi3 (SPA-NiFeOx/FeNi3) heterostructure, which is derived from the pyrolysis of MOF-on-MOF heterostructure growth triggered by graphene quantum dots (GQDs). Such SPA-NiFeOx/FeNi3 exhibits superior catalytic performance on the electrooxidation of EG (EGOR) from PET hydrolysate, with a formic acid (FA) selectivity of 91.5% and a Faradaic efficiency of 92%. The ligand effect of GQDs in both the catalyst design and improved electrocatalytic performance was studied with combined spectroscopy analysis and theoretical calculations, which revealed that such spatially separated NiFeOx and FeNi3 components by GQDs possess more active sites to anticipate in electrocatalytic EGOR, and the large sp2 domains in GQDs possess a strong electron-withdrawing ability to reduce the electron density of bonded Ni and Fe, resulting in high-valenced Niδ+/Feδ+ in FeNi3 and Ni(2+δ) in NiO, respectively. Furthermore, the coordination number of Ni and Fe centers was lowered due to the steric effect of GQDs. Therefore, the adsorption of EG on Niδ+ for cascade dehydrogenation and C–C bond cleavage led to adsorbed FA that transferred to adjacent Fe for desorption, which was promoted by the enrichment of OH on nearby Ni(2+δ) sites, along with optimized Gibbs free energy change in the multistep reaction pathway. This work provides an efficient multi-active-site catalyst for disused PET plastics valorization, thereby presenting a new approach to enhance the efficiency of PET plastics valorization reactions.

Abstract Image

NiFeOx/FeNi3异质结构中石墨烯量子点的配体效应对增强聚对苯二甲酸乙酯塑料电催化价化的影响
废旧聚对苯二甲酸乙二醇酯(PET)塑料的电催化增值为解决塑料污染和资源升级的潜在途径,但在PET衍生的乙二醇(EG)电氧化的高效催化剂的开发方面面临挑战。在此,我们提出了在fe掺杂NiO/FeNi3 (SPA-NiFeOx/FeNi3)异质结构上的金字塔阵列,该异质结构来源于石墨烯量子点(GQDs)引发的MOF-on-MOF异质结构生长的热解过程。SPA-NiFeOx/FeNi3对PET水解液中EG (EGOR)的电氧化表现出优异的催化性能,甲酸(FA)选择性为91.5%,法拉第效率为92%。结合光谱分析和理论计算,研究了GQDs在催化剂设计和提高电催化性能方面的配体效应,结果表明,GQDs在空间上分离的NiFeOx和FeNi3组分在电催化EGOR中具有更多的活性位点,并且GQDs中的大sp2结构域具有很强的吸电子能力,降低了Ni和Fe键合的电子密度。在FeNi3和NiO中分别产生了高价的Ni +/Feδ+和Ni(2+δ)。此外,由于GQDs的空间效应,降低了Ni和Fe中心的配位数。因此,EG在Ni +上的吸附进行级联脱氢和C-C键的裂解导致吸附的FA转移到邻近的Fe上进行解吸,而邻近Ni(2+δ)位点上OH−的富集促进了这一过程,并在多步反应途径中优化了吉布斯自由能变化。本研究为废弃PET塑料的增值反应提供了一种高效的多活性位点催化剂,从而为提高PET塑料的增值反应效率提供了一条新途径。
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来源期刊
Journal of Energy Chemistry
Journal of Energy Chemistry CHEMISTRY, APPLIED-CHEMISTRY, PHYSICAL
CiteScore
19.10
自引率
8.40%
发文量
3631
审稿时长
15 days
期刊介绍: The Journal of Energy Chemistry, the official publication of Science Press and the Dalian Institute of Chemical Physics, Chinese Academy of Sciences, serves as a platform for reporting creative research and innovative applications in energy chemistry. It mainly reports on creative researches and innovative applications of chemical conversions of fossil energy, carbon dioxide, electrochemical energy and hydrogen energy, as well as the conversions of biomass and solar energy related with chemical issues to promote academic exchanges in the field of energy chemistry and to accelerate the exploration, research and development of energy science and technologies. This journal focuses on original research papers covering various topics within energy chemistry worldwide, including: Optimized utilization of fossil energy Hydrogen energy Conversion and storage of electrochemical energy Capture, storage, and chemical conversion of carbon dioxide Materials and nanotechnologies for energy conversion and storage Chemistry in biomass conversion Chemistry in the utilization of solar energy
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