Masazumi Tamura, Yuna Sasano, SMA Hakim Siddiki, Masato Akatsuka, Pengru Chen, Yusuke Kita
{"title":"异相ceo2负载cu掺杂Ru催化剂催化氢解低气产物聚乙烯的化学回收","authors":"Masazumi Tamura, Yuna Sasano, SMA Hakim Siddiki, Masato Akatsuka, Pengru Chen, Yusuke Kita","doi":"10.1016/j.jcat.2025.116417","DOIUrl":null,"url":null,"abstract":"<div><div>Chemical recycling of polyolefins to valuable chemicals has a high potential to mitigate plastic problems and contributes to carbon recycling. In the previous works, we reported that CeO<sub>2</sub>- and ZrO<sub>2</sub>-supported Ru (Ru/CeO<sub>2</sub> and Ru/ZrO<sub>2</sub>) catalysts were effective for the hydrogenolysis of polyolefins such as PE, PP, and even waste PE plastics; however, the gas products were formed in ∼10 % yield. The development of effective heterogeneous catalysts that can suppress the formation of cheap gas products, particularly methane, through the incorporation of inexpensive metals into Ru is highly required to achieve high yields of valuable chemicals such as liquid and waxes. Herein, we found that 1 wt% Cu doped 1 wt% Ru/CeO<sub>2</sub>, Cu(1)-Ru(1)/CeO<sub>2</sub>, was an effective heterogeneous catalyst for the suppression of the methane formation (2.3 %, C1–C4 gas: ∼4%) at >99 % conversion in the hydrogenolysis of LDPE at 5 MPa H<sub>2</sub>, providing the high yield (96 %) of the valuable chemicals (liquid chemicals (C5-C21) + waxes (C ≥22)). The gas selectivity remains low even at a low H<sub>2</sub> pressure of 2 MPa. Based on the catalyst characterizations such as XRD, TEM, TEM-EDX, H<sub>2</sub>-TPR, XAS, and FT-IR analyses, the size of the active metal particles over Cu(1)-Ru(1)/CeO<sub>2</sub> catalyst is about 1 nm, and the addition of Cu metal into Ru/CeO<sub>2</sub> formed Ru-Cu surface alloy on the Ru particles. The formation of the small metal particles and Cu-Ru surface alloy by the addition of inexpensive Cu to Ru decreased the Ru ensemble size to suppress the consecutive C–C bond dissociation of LDPE, leading to low methane and gas yields.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116417"},"PeriodicalIF":6.5000,"publicationDate":"2025-09-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Chemical recycling of polyethylenes with low gas products by catalytic hydrogenolysis with heterogeneous CeO2-supported Cu-doped Ru catalyst\",\"authors\":\"Masazumi Tamura, Yuna Sasano, SMA Hakim Siddiki, Masato Akatsuka, Pengru Chen, Yusuke Kita\",\"doi\":\"10.1016/j.jcat.2025.116417\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Chemical recycling of polyolefins to valuable chemicals has a high potential to mitigate plastic problems and contributes to carbon recycling. In the previous works, we reported that CeO<sub>2</sub>- and ZrO<sub>2</sub>-supported Ru (Ru/CeO<sub>2</sub> and Ru/ZrO<sub>2</sub>) catalysts were effective for the hydrogenolysis of polyolefins such as PE, PP, and even waste PE plastics; however, the gas products were formed in ∼10 % yield. The development of effective heterogeneous catalysts that can suppress the formation of cheap gas products, particularly methane, through the incorporation of inexpensive metals into Ru is highly required to achieve high yields of valuable chemicals such as liquid and waxes. Herein, we found that 1 wt% Cu doped 1 wt% Ru/CeO<sub>2</sub>, Cu(1)-Ru(1)/CeO<sub>2</sub>, was an effective heterogeneous catalyst for the suppression of the methane formation (2.3 %, C1–C4 gas: ∼4%) at >99 % conversion in the hydrogenolysis of LDPE at 5 MPa H<sub>2</sub>, providing the high yield (96 %) of the valuable chemicals (liquid chemicals (C5-C21) + waxes (C ≥22)). The gas selectivity remains low even at a low H<sub>2</sub> pressure of 2 MPa. Based on the catalyst characterizations such as XRD, TEM, TEM-EDX, H<sub>2</sub>-TPR, XAS, and FT-IR analyses, the size of the active metal particles over Cu(1)-Ru(1)/CeO<sub>2</sub> catalyst is about 1 nm, and the addition of Cu metal into Ru/CeO<sub>2</sub> formed Ru-Cu surface alloy on the Ru particles. The formation of the small metal particles and Cu-Ru surface alloy by the addition of inexpensive Cu to Ru decreased the Ru ensemble size to suppress the consecutive C–C bond dissociation of LDPE, leading to low methane and gas yields.</div></div>\",\"PeriodicalId\":346,\"journal\":{\"name\":\"Journal of Catalysis\",\"volume\":\"452 \",\"pages\":\"Article 116417\"},\"PeriodicalIF\":6.5000,\"publicationDate\":\"2025-09-11\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Catalysis\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S002195172500483X\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Catalysis","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S002195172500483X","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Chemical recycling of polyethylenes with low gas products by catalytic hydrogenolysis with heterogeneous CeO2-supported Cu-doped Ru catalyst
Chemical recycling of polyolefins to valuable chemicals has a high potential to mitigate plastic problems and contributes to carbon recycling. In the previous works, we reported that CeO2- and ZrO2-supported Ru (Ru/CeO2 and Ru/ZrO2) catalysts were effective for the hydrogenolysis of polyolefins such as PE, PP, and even waste PE plastics; however, the gas products were formed in ∼10 % yield. The development of effective heterogeneous catalysts that can suppress the formation of cheap gas products, particularly methane, through the incorporation of inexpensive metals into Ru is highly required to achieve high yields of valuable chemicals such as liquid and waxes. Herein, we found that 1 wt% Cu doped 1 wt% Ru/CeO2, Cu(1)-Ru(1)/CeO2, was an effective heterogeneous catalyst for the suppression of the methane formation (2.3 %, C1–C4 gas: ∼4%) at >99 % conversion in the hydrogenolysis of LDPE at 5 MPa H2, providing the high yield (96 %) of the valuable chemicals (liquid chemicals (C5-C21) + waxes (C ≥22)). The gas selectivity remains low even at a low H2 pressure of 2 MPa. Based on the catalyst characterizations such as XRD, TEM, TEM-EDX, H2-TPR, XAS, and FT-IR analyses, the size of the active metal particles over Cu(1)-Ru(1)/CeO2 catalyst is about 1 nm, and the addition of Cu metal into Ru/CeO2 formed Ru-Cu surface alloy on the Ru particles. The formation of the small metal particles and Cu-Ru surface alloy by the addition of inexpensive Cu to Ru decreased the Ru ensemble size to suppress the consecutive C–C bond dissociation of LDPE, leading to low methane and gas yields.
期刊介绍:
The Journal of Catalysis publishes scholarly articles on both heterogeneous and homogeneous catalysis, covering a wide range of chemical transformations. These include various types of catalysis, such as those mediated by photons, plasmons, and electrons. The focus of the studies is to understand the relationship between catalytic function and the underlying chemical properties of surfaces and metal complexes.
The articles in the journal offer innovative concepts and explore the synthesis and kinetics of inorganic solids and homogeneous complexes. Furthermore, they discuss spectroscopic techniques for characterizing catalysts, investigate the interaction of probes and reacting species with catalysts, and employ theoretical methods.
The research presented in the journal should have direct relevance to the field of catalytic processes, addressing either fundamental aspects or applications of catalysis.