Daowei Zha , Shenchen Jiang , Qin Zhang , Jie Li , Zhong-Jie Jiang , Chu Qin , Xiaoning Tian , T. Maiyalagan , Zhongqing Jiang
{"title":"等离子体缺陷工程增强PtNi纳米颗粒对碱性直接甲醇燃料电池的催化活性:机理研究","authors":"Daowei Zha , Shenchen Jiang , Qin Zhang , Jie Li , Zhong-Jie Jiang , Chu Qin , Xiaoning Tian , T. Maiyalagan , Zhongqing Jiang","doi":"10.1016/j.cej.2025.166892","DOIUrl":null,"url":null,"abstract":"<div><div>The slow reaction rates of oxygen-reduction reaction (ORR) and methanol-oxidation reaction (MOR) have become one of the major problems limiting the development of alkaline direct-methanol fuel-cell (ADMFC) technology. Therefore, the rational design and development of efficient and stable ORR/MOR bifunctional catalysts are of great significance and a key step to promote the commercialization of ADMFC technology. Here, an efficient bifunctional catalyst is synthesized by twice radio-frequency (RF) plasma treatments, which is characterized by defect-rich nitrogen-doped carbon nanotubes grown on carbon cloth supporting low-valent PtNi nanoparticles (p-PtNi/p-NCFs@CC). Twice RF plasma treatments on the one hand, create more defects on the surface of p-NCFs, which could provide more active sites for loading of more p-PtNi NPs, on the other hand, the reduction of PtNi NPs into more low valence state metals improved the catalytic activity of the catalyst. Density-functional theory calculations prove that the defects generated during plasma treatment promote the deposition of PtNi NPs, enhance the charge transfer between PtNi NPs and the substrate, and improve the stability of the catalysts. The reduced oxidation state of plasma-treated PtNi NPs is shown to lower the activation energy for rate-limiting steps in both ORR and MOR. When p-PtNi/p-NCFs@CC is used as both the cathode and anode of an ADMFC, it still exhibits a peak power density of up to 85.8 mW cm<sup>−2</sup> at 80 °C with excellent stability. Compared with the conventional 20 wt% Pt/C commercial catalyst, p-PtNi/p-NCFs@CC exhibits superior and more stable ORR and MOR performance. These findings not only present a high-performance catalyst with direct applicability in ADMFCs, but more importantly, establish a fundamentally new paradigm for electrocatalyst synthesis through defect engineering and plasma-assisted fabrication.</div></div>","PeriodicalId":270,"journal":{"name":"Chemical Engineering Journal","volume":"522 ","pages":"Article 166892"},"PeriodicalIF":13.2000,"publicationDate":"2025-08-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Plasma defect engineering for enhanced catalytic activity of PtNi nanoparticles for alkaline direct methanol fuel cells: Investigation of mechanisms\",\"authors\":\"Daowei Zha , Shenchen Jiang , Qin Zhang , Jie Li , Zhong-Jie Jiang , Chu Qin , Xiaoning Tian , T. Maiyalagan , Zhongqing Jiang\",\"doi\":\"10.1016/j.cej.2025.166892\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The slow reaction rates of oxygen-reduction reaction (ORR) and methanol-oxidation reaction (MOR) have become one of the major problems limiting the development of alkaline direct-methanol fuel-cell (ADMFC) technology. Therefore, the rational design and development of efficient and stable ORR/MOR bifunctional catalysts are of great significance and a key step to promote the commercialization of ADMFC technology. Here, an efficient bifunctional catalyst is synthesized by twice radio-frequency (RF) plasma treatments, which is characterized by defect-rich nitrogen-doped carbon nanotubes grown on carbon cloth supporting low-valent PtNi nanoparticles (p-PtNi/p-NCFs@CC). Twice RF plasma treatments on the one hand, create more defects on the surface of p-NCFs, which could provide more active sites for loading of more p-PtNi NPs, on the other hand, the reduction of PtNi NPs into more low valence state metals improved the catalytic activity of the catalyst. Density-functional theory calculations prove that the defects generated during plasma treatment promote the deposition of PtNi NPs, enhance the charge transfer between PtNi NPs and the substrate, and improve the stability of the catalysts. The reduced oxidation state of plasma-treated PtNi NPs is shown to lower the activation energy for rate-limiting steps in both ORR and MOR. When p-PtNi/p-NCFs@CC is used as both the cathode and anode of an ADMFC, it still exhibits a peak power density of up to 85.8 mW cm<sup>−2</sup> at 80 °C with excellent stability. Compared with the conventional 20 wt% Pt/C commercial catalyst, p-PtNi/p-NCFs@CC exhibits superior and more stable ORR and MOR performance. These findings not only present a high-performance catalyst with direct applicability in ADMFCs, but more importantly, establish a fundamentally new paradigm for electrocatalyst synthesis through defect engineering and plasma-assisted fabrication.</div></div>\",\"PeriodicalId\":270,\"journal\":{\"name\":\"Chemical Engineering Journal\",\"volume\":\"522 \",\"pages\":\"Article 166892\"},\"PeriodicalIF\":13.2000,\"publicationDate\":\"2025-08-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Chemical Engineering Journal\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S1385894725077307\",\"RegionNum\":1,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENGINEERING, CHEMICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Chemical Engineering Journal","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S1385894725077307","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENGINEERING, CHEMICAL","Score":null,"Total":0}
Plasma defect engineering for enhanced catalytic activity of PtNi nanoparticles for alkaline direct methanol fuel cells: Investigation of mechanisms
The slow reaction rates of oxygen-reduction reaction (ORR) and methanol-oxidation reaction (MOR) have become one of the major problems limiting the development of alkaline direct-methanol fuel-cell (ADMFC) technology. Therefore, the rational design and development of efficient and stable ORR/MOR bifunctional catalysts are of great significance and a key step to promote the commercialization of ADMFC technology. Here, an efficient bifunctional catalyst is synthesized by twice radio-frequency (RF) plasma treatments, which is characterized by defect-rich nitrogen-doped carbon nanotubes grown on carbon cloth supporting low-valent PtNi nanoparticles (p-PtNi/p-NCFs@CC). Twice RF plasma treatments on the one hand, create more defects on the surface of p-NCFs, which could provide more active sites for loading of more p-PtNi NPs, on the other hand, the reduction of PtNi NPs into more low valence state metals improved the catalytic activity of the catalyst. Density-functional theory calculations prove that the defects generated during plasma treatment promote the deposition of PtNi NPs, enhance the charge transfer between PtNi NPs and the substrate, and improve the stability of the catalysts. The reduced oxidation state of plasma-treated PtNi NPs is shown to lower the activation energy for rate-limiting steps in both ORR and MOR. When p-PtNi/p-NCFs@CC is used as both the cathode and anode of an ADMFC, it still exhibits a peak power density of up to 85.8 mW cm−2 at 80 °C with excellent stability. Compared with the conventional 20 wt% Pt/C commercial catalyst, p-PtNi/p-NCFs@CC exhibits superior and more stable ORR and MOR performance. These findings not only present a high-performance catalyst with direct applicability in ADMFCs, but more importantly, establish a fundamentally new paradigm for electrocatalyst synthesis through defect engineering and plasma-assisted fabrication.
期刊介绍:
The Chemical Engineering Journal is an international research journal that invites contributions of original and novel fundamental research. It aims to provide an international platform for presenting original fundamental research, interpretative reviews, and discussions on new developments in chemical engineering. The journal welcomes papers that describe novel theory and its practical application, as well as those that demonstrate the transfer of techniques from other disciplines. It also welcomes reports on carefully conducted experimental work that is soundly interpreted. The main focus of the journal is on original and rigorous research results that have broad significance. The Catalysis section within the Chemical Engineering Journal focuses specifically on Experimental and Theoretical studies in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. These studies have industrial impact on various sectors such as chemicals, energy, materials, foods, healthcare, and environmental protection.