Polyoxometalate-Based Zinc–Organic Network as a Dual-Site Acid Catalyst for the Conversion of Polyethylene Terephthalate Plastic to Terephthalic Acid

IF 4.3 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-04-18 DOI:10.1021/acs.inorgchem.5c00408

Qian Liu, Ya-Nan Sun, Wei Yang, Yuan-Yuan Ma, Jing Du, Zhan-Gang Han

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Abstract

Chemical depolymerization and recycling of poly(ethylene terephthalate) (PET) constitute a sustainable, resource-efficient, and environmentally beneficial approach, which requires the development of efficient heterogeneous catalysts. Herein, polyoxometalate(POM)-based zinc–organic networks were synthesized as dual-site acid catalysts for the alcoholysis of PET into the value-added terephthalic acid (TPA) product, with formulas of [Zn₂(μ₂-Cl)(H₂O)₂(DTAB)₃][PW₁₂O₄₀]·4H₂O (1), [Zn₂(DTAB)₄][SiW₁₂O₄₀]·4H₂O (2), and [Zn₂(H₂O)₄(DTAB)_2.5][HBW₁₂O₄₀]·8H₂O (3) (DTAB = 1,4-di(4H-1,2,4-triazol-4-yl)benzene). Structural analysis showed that compounds 1 and 2 were composed of 2D Zn-ligand networks embedded POM clusters in an “egg-in-a-box” manner and that compound 3 consisted of a 3D POM-based host–guest framework constructed by {Zn₂(H₂O)₄(N-N)₃} units and [HBW₁₂O₄₀]^4– clusters. Three compounds incorporate the Zn²⁺ Lewis acid centers and heteropolytungstate clusters, having the acid strength order compound 3 > compound 1 > compound 2. When employed as dual-site acid catalysts, the three compounds exhibited efficient catalytic performance for PET alcoholysis into TPA with >92% conversion rate and >94% selectivity of the TPA product, along with excellent recyclability and structural stability. This work offers a novel perspective for the development of POM-based heterogeneous catalysts in the upcycling of plastic waste.

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聚金属氧酸盐基锌-有机网络作为聚对苯二甲酸塑料转化为对苯二甲酸的双位点酸催化剂

聚对苯二甲酸乙酯（PET）的化学解聚和回收是一条可持续、资源节约型和环境友好的途径，这就需要开发高效的多相催化剂。本文合成了以聚金属氧酸盐（POM）为基础的锌有机网络，作为PET醇解制备附加值对苯二甲酸（TPA）产物的双位点酸催化剂，分子式为[Zn2(μ - cl)(H2O)2(DTAB)3][PW12O40]·4H2O (1), [Zn2(DTAB)4][SiW12O40]·4H2O (2), [Zn2(H2O)4(DTAB)2.5][HBW12O40]·8H2O (3) （DTAB = 1,4-二（4h -1,2,4-三唑-4-基）苯）。结构分析表明，化合物1和2是由嵌入POM簇的二维zn配体网络以“鸡蛋在盒子里”的方式组成，化合物3是由{Zn2(H2O)4(N-N)3}单元和[HBW12O40]4 -簇构成的基于POM的三维主客体框架。三种化合物结合了Zn2+刘易斯酸中心和杂多钨酸盐簇，酸强度级为3 >；化合物1 >；化合物2。作为双位点酸催化剂时，这3种化合物表现出高效的催化性能，PET醇解制TPA的转化率为92%，TPA产物的选择性为94%，并且具有良好的可回收性和结构稳定性。这项工作为塑料垃圾升级回收中基于pom的多相催化剂的开发提供了一个新的视角。

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来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.