Yanyuan Bai , Li Zou , Jian Jiao , Yutong Gao , Cong Wang , Yanjun Dai , Yungang Wang
{"title":"高分散ceo2促进Ca-Ni复合材料耦合CO2捕集和甲烷干重整:提高循环稳定性和重整效率","authors":"Yanyuan Bai , Li Zou , Jian Jiao , Yutong Gao , Cong Wang , Yanjun Dai , Yungang Wang","doi":"10.1016/j.fuel.2025.137071","DOIUrl":null,"url":null,"abstract":"<div><div>Ni–Ca-based dual-functional materials have been widely employed in calcium looping–assisted dry reforming of methane (CaL–DRM) to enable efficient CO<sub>2</sub> capture and in situ conversion. However, their performance and operational lifetime are often severely limited by carbon deposition and Ni particle sintering during cyclic CaL–DRM processes. In this study, a Ni–Ca<sub>10</sub>Ce dual-functional material with highly dispersed CeO<sub>2</sub> was successfully synthesized via a citrate complexation method. The structural and catalytic properties of the material were systematically investigated. Characterization results revealed that the incorporation of highly dispersed CeO<sub>2</sub> significantly optimized the pore structure and, through interfacial synergy with Ni, greatly enhanced oxygen mobility. CaL–DRM cycle experiments demonstrated that at 650 °C, Ni–Ca<sub>10</sub>Ce exhibited excellent synergistic catalytic performance, achieving a hydrogen production rate of 0.827 mmol/g·min with good cyclic stability. Optimization of reaction conditions revealed that the material achieved its best catalytic performance at a CH<sub>4</sub> flow rate of 50 mL/min, with hydrogen yield increasing to 1.0 mmol/g·min. Long-term stability tests showed that after 10 CaL–DRM cycles, the CO<sub>2</sub> and CH<sub>4</sub> conversion rates decreased by only 4.6 % and 7.6 %, respectively—markedly superior to CeO<sub>2</sub>-free Ni–Ca materials. SEM analysis further confirmed that the highly dispersed CeO<sub>2</sub> on the surface effectively suppressed Ni particle sintering and carbon accumulation, serving as a key factor in ensuring the catalyst’s long-term operational stability. This study provides a novel strategy for material development and performance enhancement in the CaL–DRM system.</div></div>","PeriodicalId":325,"journal":{"name":"Fuel","volume":"406 ","pages":"Article 137071"},"PeriodicalIF":7.5000,"publicationDate":"2025-10-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"High-dispersion CeO2-promoted Ca-Ni composites for coupled CO2 capture and methane dry reforming: Improved cycle stability and reforming efficiency\",\"authors\":\"Yanyuan Bai , Li Zou , Jian Jiao , Yutong Gao , Cong Wang , Yanjun Dai , Yungang Wang\",\"doi\":\"10.1016/j.fuel.2025.137071\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Ni–Ca-based dual-functional materials have been widely employed in calcium looping–assisted dry reforming of methane (CaL–DRM) to enable efficient CO<sub>2</sub> capture and in situ conversion. However, their performance and operational lifetime are often severely limited by carbon deposition and Ni particle sintering during cyclic CaL–DRM processes. In this study, a Ni–Ca<sub>10</sub>Ce dual-functional material with highly dispersed CeO<sub>2</sub> was successfully synthesized via a citrate complexation method. The structural and catalytic properties of the material were systematically investigated. Characterization results revealed that the incorporation of highly dispersed CeO<sub>2</sub> significantly optimized the pore structure and, through interfacial synergy with Ni, greatly enhanced oxygen mobility. CaL–DRM cycle experiments demonstrated that at 650 °C, Ni–Ca<sub>10</sub>Ce exhibited excellent synergistic catalytic performance, achieving a hydrogen production rate of 0.827 mmol/g·min with good cyclic stability. Optimization of reaction conditions revealed that the material achieved its best catalytic performance at a CH<sub>4</sub> flow rate of 50 mL/min, with hydrogen yield increasing to 1.0 mmol/g·min. Long-term stability tests showed that after 10 CaL–DRM cycles, the CO<sub>2</sub> and CH<sub>4</sub> conversion rates decreased by only 4.6 % and 7.6 %, respectively—markedly superior to CeO<sub>2</sub>-free Ni–Ca materials. SEM analysis further confirmed that the highly dispersed CeO<sub>2</sub> on the surface effectively suppressed Ni particle sintering and carbon accumulation, serving as a key factor in ensuring the catalyst’s long-term operational stability. This study provides a novel strategy for material development and performance enhancement in the CaL–DRM system.</div></div>\",\"PeriodicalId\":325,\"journal\":{\"name\":\"Fuel\",\"volume\":\"406 \",\"pages\":\"Article 137071\"},\"PeriodicalIF\":7.5000,\"publicationDate\":\"2025-10-10\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Fuel\",\"FirstCategoryId\":\"5\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0016236125027966\",\"RegionNum\":1,\"RegionCategory\":\"工程技术\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"ENERGY & FUELS\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Fuel","FirstCategoryId":"5","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0016236125027966","RegionNum":1,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"ENERGY & FUELS","Score":null,"Total":0}
引用次数: 0
摘要
ni - ca基双功能材料已广泛应用于钙环辅助甲烷干重整(CaL-DRM)中,以实现高效的CO2捕获和原位转化。然而,在循环CaL-DRM过程中,它们的性能和使用寿命往往受到碳沉积和Ni颗粒烧结的严重限制。本研究通过柠檬酸盐络合法制备了具有高度分散CeO2的Ni-Ca10Ce双功能材料。系统地研究了该材料的结构和催化性能。表征结果表明,高度分散的CeO2的掺入显著优化了孔隙结构,并通过与Ni的界面协同作用,大大提高了氧的迁移率。CaL-DRM循环实验表明,在650℃时,Ni-Ca10Ce表现出优异的协同催化性能,产氢速率为0.827 mmol/g·min,循环稳定性好。反应条件优化表明,CH4流量为50 mL/min时,材料的催化性能最佳,产氢率可达1.0 mmol/g·min。长期稳定性试验表明,经过10次CaL-DRM循环后,CO2和CH4转化率仅下降4.6%和7.6%,明显优于无ceo2的Ni-Ca材料。SEM分析进一步证实,表面高度分散的CeO2有效抑制了Ni颗粒的烧结和碳的积累,是保证催化剂长期稳定运行的关键因素。本研究为CaL-DRM系统的材料开发和性能提升提供了一种新的策略。
High-dispersion CeO2-promoted Ca-Ni composites for coupled CO2 capture and methane dry reforming: Improved cycle stability and reforming efficiency
Ni–Ca-based dual-functional materials have been widely employed in calcium looping–assisted dry reforming of methane (CaL–DRM) to enable efficient CO2 capture and in situ conversion. However, their performance and operational lifetime are often severely limited by carbon deposition and Ni particle sintering during cyclic CaL–DRM processes. In this study, a Ni–Ca10Ce dual-functional material with highly dispersed CeO2 was successfully synthesized via a citrate complexation method. The structural and catalytic properties of the material were systematically investigated. Characterization results revealed that the incorporation of highly dispersed CeO2 significantly optimized the pore structure and, through interfacial synergy with Ni, greatly enhanced oxygen mobility. CaL–DRM cycle experiments demonstrated that at 650 °C, Ni–Ca10Ce exhibited excellent synergistic catalytic performance, achieving a hydrogen production rate of 0.827 mmol/g·min with good cyclic stability. Optimization of reaction conditions revealed that the material achieved its best catalytic performance at a CH4 flow rate of 50 mL/min, with hydrogen yield increasing to 1.0 mmol/g·min. Long-term stability tests showed that after 10 CaL–DRM cycles, the CO2 and CH4 conversion rates decreased by only 4.6 % and 7.6 %, respectively—markedly superior to CeO2-free Ni–Ca materials. SEM analysis further confirmed that the highly dispersed CeO2 on the surface effectively suppressed Ni particle sintering and carbon accumulation, serving as a key factor in ensuring the catalyst’s long-term operational stability. This study provides a novel strategy for material development and performance enhancement in the CaL–DRM system.
期刊介绍:
The exploration of energy sources remains a critical matter of study. For the past nine decades, fuel has consistently held the forefront in primary research efforts within the field of energy science. This area of investigation encompasses a wide range of subjects, with a particular emphasis on emerging concerns like environmental factors and pollution.