Collaborative Research: Design of a Novel Photo-Thermo-Catalyst for Enhanced Activity and Stability of Dry Reforming of Methane

合作研究：设计新型光热催化剂以增强甲烷干重整的活性和稳定性

• 批准号: 1924466
• 负责人: Ying Li
• 金额: $ 32.8万
• 依托单位: Texas A&M Engineering Experiment Station
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-09-01 至 2024-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1924466&HistoricalAwards=false
• 关键词: Collaborative; Research; Design; Novel; Photo

Waste gases containing methane (CH4) and carbon dioxide (CO2) are produced from sources such as shale oil recovery, landfills, poultry and livestock farms, and other biogas sources. One way to upgrade those gases is to react them in the presence of catalysts to transform them into simple gases such as carbon monoxide (CO) and hydrogen (H2) that can be further processed to a wide range of chemicals and fuels. The catalyzed reaction between methane and carbon dioxide requires extremely high temperatures which makes it unattractive from an energy consumption standpoint. An alternative approach is to utilize a combination of direct sunlight irradiation and heat generated via solar energy collectors to react the gases via simultaneous photocatalysis and thermal catalysis in a sustainable process driven solely by the sun's energy. The project explores that concept using a novel approach known as thermo-photo-catalytic dry reforming of methane (DRM). Specifically, the project will focus on catalyst designs that combine direct photocatalysis with thermal catalysis to achieve stable, highly-efficient DRM at temperatures much lower than those based on conventional fossil-fuel thermal catalysis alone. The technology can potentially play a significant role in sustainably meeting our nation's future energy needs while simultaneously transforming the greenhouse gases - CH4 and CO2 - to useful fuels and chemicals.The project will investigate several novel aspects of thermo-photo-catalytic DRM, including: (1) fabricating novel and stable catalysts that promote synergy between the photo- and thermo-catalytic effects via integration of a photocatalytically active support, inexpensive metal nanocatalysts dispersed on the support, and promoters to enhance catalytic activity and stability; (2) designing innovative nanostructures, i.e. an ultrathin porous overcoat on the catalyst via atomic layer deposition (ALD) to mitigate metal sintering and prevent coke formation; (3) understanding the fundamental mechanism of photo-thermo-catalysis at elevated temperatures through a combination of in situ DRIFTS (diffuse reflectance FTIR) spectroscopy, GC/MS measurement of the catalyst activity, and experiments using isotopically labeled CO2 and CH4 molecules; and (4) elucidating catalyst structure-activity-stability relationships through operando studies of metal valence, nanoparticle size, and overcoat pore structure changes, carried out utilizing in situ X-ray scattering, X-ray diffraction, and X-ray absorption spectroscopy at the Advanced Photon Source of Argonne National Laboratory. This research will advance fundamental understanding in the interdisciplinary areas of heterogeneous catalysis, surface chemistry, nanoscience, and spectroscopy. In addition to the technical component of the research, the project will be supported by several programs at both institutions aimed at providing both high-school students and their teachers opportunities to develop research skills.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

含有甲烷（CH4）和二氧化碳（CO2）的废气是由页岩石油回收，垃圾填埋场，家禽和牲畜农场以及其他沼气来源产生的。 升级这些气体的一种方法是在存在催化剂的情况下反应它们，以将它们转化为简单的气体，例如一氧化碳（CO）和氢（H2），这些气体可以进一步加工到广泛的化学物质和燃料中。 甲烷和二氧化碳之间的催化反应需要极高的温度，这使其从能耗的角度没有吸引力。 另一种方法是利用直接阳光照射和通过太阳能收集器产生的热量的组合，通过同时光催化和热催化在可持续过程中反应气体，仅由太阳的能量驱动。 该项目使用一种新颖的方法探索了这种概念，称为甲烷（DRM）的热催化催化干燥的改革。 具体而言，该项目将集中于将直接光催化与热催化相结合的催化剂设计，以在温度下实现稳定的高效DRM，远低于基于常规化石燃料燃料热催化的催化剂。 该技术在可持续满足我们国家的未来能源需求方面可能发挥重要作用，同时将温室气体（CH4和CO2）转换为有用的燃料和化学物质。该项目将研究热能催化性DRM的几个新颖方面纳米催化剂分散在支撑上，并启动子增强催化活性和稳定性； （2）设计创新的纳米结构，即通过原子层沉积（ALD）在催化剂上的超薄多孔大衣，以减轻金属烧结并防止焦炭形成； （3）通过原位漂移（弥漫性反射率FTIR）光谱，催化剂活性的GC/MS测量以及使用同位素标记的CO2和CH4分子的实验来了解升高温度下光催化的基本机制； （4）通过对原位X射线散射，X射线衍射和X射线吸收光谱镜头进行的，通过对金属价，纳米颗粒大小的操作研究，纳米颗粒大小和大衣孔结构变化来阐明催化剂结构 - 活性稳定关系。这项研究将在异质催化，表面化学，纳米科学和光谱学的跨学科领域提高基本理解。 除研究的技术组成部分外，该项目还将得到两个机构的几个计划的支持，旨在为高中生及其教师提供发展研究技能的机会。该奖项反映了NSF的法定任务，并被认为是值得通过基金会的知识分子优点和更广泛的影响来通过评估来支持的。

项目成果

Development of stable La0.9Ce0.1NiO3 perovskite catalyst for enhanced photothermochemical dry reforming of methane

• DOI: 10.1016/j.jcou.2022.102317
• 发表时间: 2023-01
• 期刊: Journal of CO2 Utilization
• 影响因子: 7.7
• 作者: Zichen Du;Cullen R Petru;Xiaokun Yang;Fan Chen;Siyuan Fang;Fuping Pan;Yang Gang;Hongcai Zhou;Y. Hu;Ying Li

Syngas production at a near-unity H 2 /CO ratio from photo-thermo-chemical dry reforming of methane on a Pt decorated Al 2 O 3 –CeO 2 catalyst

在 Pt 修饰的 Al 2 O 3 →CeO 2 催化剂上通过光热化学干重整甲烷以接近一致的 H 2 /CO 比例生产合成气

• DOI: 10.1039/d1ta10088b
• 发表时间: 2022
• 期刊: Journal of Materials Chemistry A
• 影响因子: 11.9
• 作者: Feng, Xuhui;Du, Zichen;Sarnello, Erik;Deng, Wei;Petru, Cullen R.;Fang, Lingzhe;Li, Tao;Li, Ying
• 通讯作者: Li, Ying

Efficient Photothermochemical Dry Reforming of Methane over Ni Supported on ZrO2 with CeO2 Incorporation

• DOI: 10.1016/j.cattod.2022.05.014
• 发表时间: 2022-05
• 期刊: Catalysis Today
• 影响因子: 5.3
• 作者: Zichen Du;Fuping Pan;Xiaokun Yang;Lingzhe Fang;Yang Gang;Siyuan Fang;Tao Li;Y. Hu;Ying Li

Integrating photocatalysis and thermocatalysis to enable efficient CO2 reforming of methane on Pt supported CeO2 with Zn doping and atomic layer deposited MgO overcoating

• DOI: 10.1016/j.apcatb.2019.118189
• 发表时间: 2020
• 期刊: Applied Catalysis B-environmental
• 影响因子: 22.1
• 作者: Fuping Pan;Xianmei Xiang;Zichen Du;Erik Sarnello;Tao Li;Ying Li