{"title":"促进*OH吸附促进C-C键裂解，用于高效的聚对苯二甲酸乙二醇酯的电化学升级回收","authors":"Jinyong Sun, Binkai Shi, Shuixing Dai, Lei Chu, Huanlei Wang, Minghua Huang","doi":"10.1021/acscatal.4c05352","DOIUrl":null,"url":null,"abstract":"The electrochemical oxidation of ethylene glycol (EG) derived from polyethylene terephthalate (PET) plastic into value-added chemicals, coupled with hydrogen evolution, offers a promising approach to addressing plastic pollution. However, the mechanisms by which the adsorption of key reaction intermediates affects the EG oxidation reaction (EGOR) are not well understood. To investigate this, we synthesized two model catalysts: amorphous-phase CoNiOOH/NF and CoNiOOH–Ni<sub>3</sub>S<sub>2</sub>/NF with an amorphous/crystalline interface. Detailed characterizations and theoretical calculations demonstrate that the amorphous/crystalline interface in CoNiOOH–Ni<sub>3</sub>S<sub>2</sub>/NF shifts the d-band center upward, enhancing the adsorption of EG and *OH compared to amorphous CoNiOOH/NF. Enhanced *OH adsorption is crucial for promoting C–C bond cleavage and subsequent dehydrogenation. In situ electrochemical infrared absorption spectroscopy (IRAS) and theoretical calculations reveal that formate (FA) is primarily formed through cleavage of the C–C bond in glycolic acid, followed by oxidation. Notably, CoNiOOH–Ni<sub>3</sub>S<sub>2</sub>/NF achieves industrial-level current densities of 500 mA cm<sup>–2</sup> at an ultralow potential of 1.45 V vs RHE, with a Faradaic efficiency (FE) of 96.6% and FA productivity of 3.14 mmol cm<sup>–2</sup> h<sup>–1</sup> at 1.70 V vs RHE. This study offers valuable insights for designing efficient heterojunction catalysts for the electrochemical upcycling of PET plastics.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"75 1","pages":""},"PeriodicalIF":13.1000,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Promoted *OH Adsorption Facilitates C–C Bond Cleavage for Efficient Electrochemical Upcycling of Polyethylene Terephthalate\",\"authors\":\"Jinyong Sun, Binkai Shi, Shuixing Dai, Lei Chu, Huanlei Wang, Minghua Huang\",\"doi\":\"10.1021/acscatal.4c05352\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The electrochemical oxidation of ethylene glycol (EG) derived from polyethylene terephthalate (PET) plastic into value-added chemicals, coupled with hydrogen evolution, offers a promising approach to addressing plastic pollution. However, the mechanisms by which the adsorption of key reaction intermediates affects the EG oxidation reaction (EGOR) are not well understood. To investigate this, we synthesized two model catalysts: amorphous-phase CoNiOOH/NF and CoNiOOH–Ni<sub>3</sub>S<sub>2</sub>/NF with an amorphous/crystalline interface. Detailed characterizations and theoretical calculations demonstrate that the amorphous/crystalline interface in CoNiOOH–Ni<sub>3</sub>S<sub>2</sub>/NF shifts the d-band center upward, enhancing the adsorption of EG and *OH compared to amorphous CoNiOOH/NF. Enhanced *OH adsorption is crucial for promoting C–C bond cleavage and subsequent dehydrogenation. In situ electrochemical infrared absorption spectroscopy (IRAS) and theoretical calculations reveal that formate (FA) is primarily formed through cleavage of the C–C bond in glycolic acid, followed by oxidation. Notably, CoNiOOH–Ni<sub>3</sub>S<sub>2</sub>/NF achieves industrial-level current densities of 500 mA cm<sup>–2</sup> at an ultralow potential of 1.45 V vs RHE, with a Faradaic efficiency (FE) of 96.6% and FA productivity of 3.14 mmol cm<sup>–2</sup> h<sup>–1</sup> at 1.70 V vs RHE. This study offers valuable insights for designing efficient heterojunction catalysts for the electrochemical upcycling of PET plastics.\",\"PeriodicalId\":9,\"journal\":{\"name\":\"ACS Catalysis \",\"volume\":\"75 1\",\"pages\":\"\"},\"PeriodicalIF\":13.1000,\"publicationDate\":\"2024-12-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"ACS Catalysis \",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1021/acscatal.4c05352\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Catalysis ","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acscatal.4c05352","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
从聚对苯二甲酸乙二醇酯（PET）塑料中提取的乙二醇（EG）电化学氧化成增值化学品，再加上氢的释放，为解决塑料污染提供了一种有前途的方法。然而，关键反应中间体吸附影响EG氧化反应（EGOR）的机理尚不清楚。为此，我们合成了两种模型催化剂：非晶相CoNiOOH/NF和具有非晶/晶界面的CoNiOOH - ni3s2 /NF。详细的表征和理论计算表明，与非晶CoNiOOH/NF相比，CoNiOOH - ni3s2 /NF中的非晶/晶界面使d波段中心向上移动，增强了对EG和*OH的吸附。增强的*OH吸附对促进C-C键裂解和随后的脱氢至关重要。原位电化学红外吸收光谱（IRAS）和理论计算表明，甲酸酯（FA）主要是通过乙醇酸中C-C键的裂解生成，然后氧化生成。值得注意的是，conioh - ni3s2 /NF在1.45 V / RHE的超低电位下实现了500 mA cm-2的工业级电流密度，法拉第效率（FE）为96.6%，FA生产率为3.14 mmol cm-2 h-1。该研究为设计高效的异质结催化剂用于PET塑料的电化学升级回收提供了有价值的见解。
Promoted *OH Adsorption Facilitates C–C Bond Cleavage for Efficient Electrochemical Upcycling of Polyethylene Terephthalate
The electrochemical oxidation of ethylene glycol (EG) derived from polyethylene terephthalate (PET) plastic into value-added chemicals, coupled with hydrogen evolution, offers a promising approach to addressing plastic pollution. However, the mechanisms by which the adsorption of key reaction intermediates affects the EG oxidation reaction (EGOR) are not well understood. To investigate this, we synthesized two model catalysts: amorphous-phase CoNiOOH/NF and CoNiOOH–Ni3S2/NF with an amorphous/crystalline interface. Detailed characterizations and theoretical calculations demonstrate that the amorphous/crystalline interface in CoNiOOH–Ni3S2/NF shifts the d-band center upward, enhancing the adsorption of EG and *OH compared to amorphous CoNiOOH/NF. Enhanced *OH adsorption is crucial for promoting C–C bond cleavage and subsequent dehydrogenation. In situ electrochemical infrared absorption spectroscopy (IRAS) and theoretical calculations reveal that formate (FA) is primarily formed through cleavage of the C–C bond in glycolic acid, followed by oxidation. Notably, CoNiOOH–Ni3S2/NF achieves industrial-level current densities of 500 mA cm–2 at an ultralow potential of 1.45 V vs RHE, with a Faradaic efficiency (FE) of 96.6% and FA productivity of 3.14 mmol cm–2 h–1 at 1.70 V vs RHE. This study offers valuable insights for designing efficient heterojunction catalysts for the electrochemical upcycling of PET plastics.
期刊介绍：
ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels.
The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.
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