Desheng Su , Hualin Chen , Qihao Yang , Hao Liu , Mengting Lv , Yayun Zhao , Junjie Zhou , Qiuju Zhang , Zhiyi Lu , Liang Chen
{"title":"在二胺平台的帮助下,刻面工程 CeO2 上的受挫路易斯对促进了低浓度 CO2 向环状脲的转化","authors":"Desheng Su , Hualin Chen , Qihao Yang , Hao Liu , Mengting Lv , Yayun Zhao , Junjie Zhou , Qiuju Zhang , Zhiyi Lu , Liang Chen","doi":"10.1016/j.jcou.2024.102793","DOIUrl":null,"url":null,"abstract":"<div><p>The development of efficient processes for value-added utilization of low-concentration CO<sub>2</sub> is an on-going challenge. In this work, we present a sequential system based on diamine platforms for the direct utilization of low-concentration sources of CO<sub>2</sub> (≤15%) in the production of cyclic ureas. Specifically, the low-concentration CO<sub>2</sub> is captured by ethylenediamine to form ethylenediamine carbamate (EDA-CA), which subsequently undergoes the intramolecular dehydration to give ethyleneurea (EU) in the presence of frustrated Lewis pairs (FLPs) on the facet-engineered CeO<sub>2</sub>. Remarkably, the productivity of EU obtained from EDA-CA in the sequential system (9.5 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup>) is ∼4 times higher compared to the traditional catalytic system (2.4 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup>) using ethylenediamine and pure CO<sub>2</sub> (3 MPa). Density functional theory calculations demonstrated that the FLPs on facet-engineered CeO<sub>2</sub> significantly reduce the energy barrier for the nucleophilic attack of N-containing segment towards the carbonyl carbon in EDA-CA (rate-limiting step), ultimately optimizing the intramolecular cyclization efficiency of EDA-CA. This work not only provides an innovation tandem approach that enables the production of cyclic ureas from low-concentration CO<sub>2</sub>, but also opens up a promising avenue for the direct utilization of low-concentration CO<sub>2</sub> for value-added applications in the future.</p></div>","PeriodicalId":350,"journal":{"name":"Journal of CO2 Utilization","volume":null,"pages":null},"PeriodicalIF":7.2000,"publicationDate":"2024-05-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2212982024001288/pdfft?md5=b7a316e33dc3fecd5b067b3994ea5cbf&pid=1-s2.0-S2212982024001288-main.pdf","citationCount":"0","resultStr":"{\"title\":\"Frustrated Lewis pairs on facet-engineered CeO2 boost the conversion of low-concentration CO2 into cyclic ureas with assistance of diamine platforms\",\"authors\":\"Desheng Su , Hualin Chen , Qihao Yang , Hao Liu , Mengting Lv , Yayun Zhao , Junjie Zhou , Qiuju Zhang , Zhiyi Lu , Liang Chen\",\"doi\":\"10.1016/j.jcou.2024.102793\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>The development of efficient processes for value-added utilization of low-concentration CO<sub>2</sub> is an on-going challenge. In this work, we present a sequential system based on diamine platforms for the direct utilization of low-concentration sources of CO<sub>2</sub> (≤15%) in the production of cyclic ureas. Specifically, the low-concentration CO<sub>2</sub> is captured by ethylenediamine to form ethylenediamine carbamate (EDA-CA), which subsequently undergoes the intramolecular dehydration to give ethyleneurea (EU) in the presence of frustrated Lewis pairs (FLPs) on the facet-engineered CeO<sub>2</sub>. Remarkably, the productivity of EU obtained from EDA-CA in the sequential system (9.5 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup>) is ∼4 times higher compared to the traditional catalytic system (2.4 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup>) using ethylenediamine and pure CO<sub>2</sub> (3 MPa). Density functional theory calculations demonstrated that the FLPs on facet-engineered CeO<sub>2</sub> significantly reduce the energy barrier for the nucleophilic attack of N-containing segment towards the carbonyl carbon in EDA-CA (rate-limiting step), ultimately optimizing the intramolecular cyclization efficiency of EDA-CA. This work not only provides an innovation tandem approach that enables the production of cyclic ureas from low-concentration CO<sub>2</sub>, but also opens up a promising avenue for the direct utilization of low-concentration CO<sub>2</sub> for value-added applications in the future.</p></div>\",\"PeriodicalId\":350,\"journal\":{\"name\":\"Journal of CO2 Utilization\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":7.2000,\"publicationDate\":\"2024-05-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S2212982024001288/pdfft?md5=b7a316e33dc3fecd5b067b3994ea5cbf&pid=1-s2.0-S2212982024001288-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of CO2 Utilization\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2212982024001288\",\"RegionNum\":2,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of CO2 Utilization","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2212982024001288","RegionNum":2,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Frustrated Lewis pairs on facet-engineered CeO2 boost the conversion of low-concentration CO2 into cyclic ureas with assistance of diamine platforms
The development of efficient processes for value-added utilization of low-concentration CO2 is an on-going challenge. In this work, we present a sequential system based on diamine platforms for the direct utilization of low-concentration sources of CO2 (≤15%) in the production of cyclic ureas. Specifically, the low-concentration CO2 is captured by ethylenediamine to form ethylenediamine carbamate (EDA-CA), which subsequently undergoes the intramolecular dehydration to give ethyleneurea (EU) in the presence of frustrated Lewis pairs (FLPs) on the facet-engineered CeO2. Remarkably, the productivity of EU obtained from EDA-CA in the sequential system (9.5 mmol·gcat−1·h−1) is ∼4 times higher compared to the traditional catalytic system (2.4 mmol·gcat−1·h−1) using ethylenediamine and pure CO2 (3 MPa). Density functional theory calculations demonstrated that the FLPs on facet-engineered CeO2 significantly reduce the energy barrier for the nucleophilic attack of N-containing segment towards the carbonyl carbon in EDA-CA (rate-limiting step), ultimately optimizing the intramolecular cyclization efficiency of EDA-CA. This work not only provides an innovation tandem approach that enables the production of cyclic ureas from low-concentration CO2, but also opens up a promising avenue for the direct utilization of low-concentration CO2 for value-added applications in the future.
期刊介绍:
The Journal of CO2 Utilization offers a single, multi-disciplinary, scholarly platform for the exchange of novel research in the field of CO2 re-use for scientists and engineers in chemicals, fuels and materials.
The emphasis is on the dissemination of leading-edge research from basic science to the development of new processes, technologies and applications.
The Journal of CO2 Utilization publishes original peer-reviewed research papers, reviews, and short communications, including experimental and theoretical work, and analytical models and simulations.