Phosphorus-substituted atomically dispersed Rh-N3P1 sites for efficient promotion in CO2 hydrogenation towards ethanol production

IF 20.2 1区化学 Q1 CHEMISTRY, PHYSICAL

Applied Catalysis B: Environmental Pub Date : 2024-01-12 DOI:10.1016/j.apcatb.2024.123730

Ke Zheng, Yufeng Li, Bing Liu, Jie Chen, Yuebing Xu, Zaijun Li, Xiaohao Liu

{"title":"Phosphorus-substituted atomically dispersed Rh-N3P1 sites for efficient promotion in CO2 hydrogenation towards ethanol production","authors":"Ke Zheng, Yufeng Li, Bing Liu, Jie Chen, Yuebing Xu, Zaijun Li, Xiaohao Liu","doi":"10.1016/j.apcatb.2024.123730","DOIUrl":null,"url":null,"abstract":"<div>Ethanol synthesis through CO2 hydrogenation has shown great promise in contributing to carbon neutrality. Herein, we for the first time present the phosphorus-substitution of atomically dispersed Rh-N4 sites for the title reaction. The as-formed Rh-N3P1 sites enable the reaction product notably switching from nearly total methanol (91.3%) towards major ethanol (81.8%) with a high TOF of 420.7 h−1. This outstanding promotion in both ethanol formation and CO2 conversion (69% higher) could be assigned to the donation of electron from P atom effectively weakening C-O bond in CH3OH* , facilitating its cleavage into CH3 * , and enabling the coupling between CO* and CH3 * . The presence of Rh-P site pair assists C-O bond activation with a longer bond length owing to a strong affinity of P atom to O atom in CH3OH* . This research underscores the importance of tuning the coordination and electronic environment of active metal sites for site pair synergistic catalysis.</div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"346 ","pages":"Article 123730"},"PeriodicalIF":20.2000,"publicationDate":"2024-01-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Applied Catalysis B: Environmental","FirstCategoryId":"1","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926337324000419","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

Abstract

Ethanol synthesis through CO₂ hydrogenation has shown great promise in contributing to carbon neutrality. Herein, we for the first time present the phosphorus-substitution of atomically dispersed Rh-N₄ sites for the title reaction. The as-formed Rh-N₃P₁ sites enable the reaction product notably switching from nearly total methanol (91.3%) towards major ethanol (81.8%) with a high TOF of 420.7 h⁻¹. This outstanding promotion in both ethanol formation and CO₂ conversion (69% higher) could be assigned to the donation of electron from P atom effectively weakening C-O bond in CH₃OH* , facilitating its cleavage into CH₃ * , and enabling the coupling between CO* and CH₃ * . The presence of Rh-P site pair assists C-O bond activation with a longer bond length owing to a strong affinity of P atom to O atom in CH₃OH* . This research underscores the importance of tuning the coordination and electronic environment of active metal sites for site pair synergistic catalysis.

Abstract Image

查看原文本刊更多论文

磷取代原子分散的 Rh-N3P1 位点可有效促进二氧化碳加氢制取乙醇

通过二氧化碳加氢合成乙醇有望实现碳中和。在此，我们首次提出了将磷取代原子分散的 Rh-N4 位点用于标题反应的方法。所形成的 Rh-N3P1 位点使反应产物从几乎完全的甲醇（91.3%）明显转向主要的乙醇（81.8%），TOF 高达 420.7 h-1。乙醇形成和 CO2 转化率（高出 69%）的显著提高可归因于 P 原子提供的电子有效削弱了 CH3OH* 中的 C-O 键，促进其裂解为 CH3*，并使 CO* 和 CH3* 得以耦合。由于 P 原子与 CH3OH* 中的 O 原子有很强的亲和力，Rh-P 位点对的存在有助于 C-O 键的活化，从而延长了键长。这项研究强调了调整活性金属位点的配位和电子环境对于位点对协同催化的重要性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文求助全文

来源期刊

Applied Catalysis B: Environmental 环境科学-工程：化工

CiteScore

38.60

自引率

6.30%

发文量

1117

审稿时长

24 days

期刊介绍： Applied Catalysis B: Environment and Energy (formerly Applied Catalysis B: Environmental) is a journal that focuses on the transition towards cleaner and more sustainable energy sources. The journal's publications cover a wide range of topics, including: 1.Catalytic elimination of environmental pollutants such as nitrogen oxides, carbon monoxide, sulfur compounds, chlorinated and other organic compounds, and soot emitted from stationary or mobile sources. 2.Basic understanding of catalysts used in environmental pollution abatement, particularly in industrial processes. 3.All aspects of preparation, characterization, activation, deactivation, and regeneration of novel and commercially applicable environmental catalysts. 4.New catalytic routes and processes for the production of clean energy, such as hydrogen generation via catalytic fuel processing, and new catalysts and electrocatalysts for fuel cells. 5.Catalytic reactions that convert wastes into useful products. 6.Clean manufacturing techniques that replace toxic chemicals with environmentally friendly catalysts. 7.Scientific aspects of photocatalytic processes and a basic understanding of photocatalysts as applied to environmental problems. 8.New catalytic combustion technologies and catalysts. 9.New catalytic non-enzymatic transformations of biomass components. The journal is abstracted and indexed in API Abstracts, Research Alert, Chemical Abstracts, Web of Science, Theoretical Chemical Engineering Abstracts, Engineering, Technology & Applied Sciences, and others.