Transition metal controlled nitrogen chemistry in zeolite and protein environments using a unified quantum embedding model

使用统一的量子嵌入模型控制沸石和蛋白质环境中的过渡金属氮化学

• 批准号: EP/R001847/1
• 负责人: Thomas Keal
• 金额: $ 130.24万
• 依托单位: Science and Technology Facilities Council
• 依托单位国家: 英国
• 项目类别: Research Grant
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=EP%2FR001847%2F1
• 关键词: Transition; metal; controlled; nitrogen; chemistry

Nitrogen compounds play a crucial role in the earth's ecosystems, being continually converted from one form to another as they pass from the atmosphere to living organisms on land and in the sea. Nitric oxide gas (NO), for example, is a key intermediate in the global nitrogen cycle, and plays important roles in many processes in almost all forms of life, often acting as a signalling molecule. However, emissions of NO and the toxic gas nitrogen dioxide (collectively known as NOx) from heavy industry and motor vehicles alter the composition of nitrogen compounds in the atmosphere and are highly damaging both directly and indirectly to the human respiratory system. The removal of NOx from exhaust emissions is a pressing environmental concern and an important target for industrial catalysis research, an area of extreme importance to the UK economy.We propose to study the chemistry of nitrogen oxides in biological and industrial environments where a full understanding of how the gases are controlled is crucial but still lacking. In both cases the chemistry is controlled by transition metals: cytochrome c' proteins have evolved an extraordinary degree of control of NO through binding to an iron complex which discriminates against other diatomic gases, while in zeolite catalysts (microporous aluminosilicate structures) NOx gases can be converted into safer by-products at copper centres through the addition of ammonia in a process known as selective catalytic reduction (SCR). The precise mechanisms, however, are not currently proven.We will investigate the chemistry of nitrogen dioxide and nitrogen oxide in both systems by computational simulations performed on high performance clusters. The resulting data will be used to model spectroscopic signatures, i.e. how electromagnetic radiation (such as light or X-rays) interacts with matter. These will be compared with the results of infrared, Raman, UV-visible and X-ray absorption experiments on the two systems to better understand the processes involved in the chemical reactions, which will inform the future design of improved zeolite catalysts and bioengineered proteins.We will use quantum mechanical/molecular mechanical (QM/MM) modelling to identify the reaction mechanisms and calculate spectroscopic signatures of the two systems. In this approach the zeolite and protein active sites will be treated using a highly accurate, but computationally expensive, quantum mechanical level of theory, embedded in an environment described by an efficient classical calculation. New QM/MM methods will be implemented that can enable larger QM regions to be calculated and more accurate spectroscopic signatures including anharmonic vibrational effects. Importantly, our approach for combining computational modelling with experimental results will be generally applicable to any chemical processes in complex systems, including other industrial catalysts and biomolecules.

氮化合物在地球的生态系统中起着至关重要的作用，当它们从大气层传递到陆地和海洋中的生物体时，它们不断地从一种形式转化为另一种形式。例如，一氧化氮气体（NO）是全球氮循环的关键中间体，在几乎所有生命形式的许多过程中发挥着重要作用，通常作为信号分子。然而，来自重工业和机动车辆的NO和有毒气体二氧化氮（统称为NOx）的排放改变了大气中氮化合物的组成，并且直接和间接地对人类呼吸系统造成高度损害。从废气排放中去除氮氧化物是一个紧迫的环境问题和工业催化研究的一个重要目标，这是一个对英国经济极其重要的领域，我们建议研究氮氧化物在生物和工业环境中的化学，充分了解如何控制气体是至关重要的，但仍然缺乏。在这两种情况下，化学反应都是由过渡金属控制的：细胞色素c'蛋白质通过与铁络合物结合来控制NO，从而对其他双原子气体进行区分，而在沸石催化剂（微孔铝硅酸盐结构）中，NOx气体可以通过在称为选择性催化还原（SCR）的过程中添加氨在铜中心转化为更安全的副产品。精确的机制，然而，目前还没有得到证实。我们将调查化学的二氧化氮和氮氧化物在这两个系统中进行的高性能集群的计算模拟。由此产生的数据将用于模拟光谱特征，即电磁辐射（如光或X射线）如何与物质相互作用。这些结果将与两个体系的红外、拉曼、紫外-可见光和X射线吸收实验结果进行比较，以更好地理解化学反应过程，这将为未来改进沸石催化剂和生物工程蛋白质的设计提供信息。我们将使用量子力学/分子力学（QM/MM）模型来识别反应机理并计算两个体系的光谱特征。在这种方法中，沸石和蛋白质活性位点将使用高度精确但计算昂贵的量子力学理论水平来处理，嵌入在由有效的经典计算描述的环境中。新的QM/MM方法将被实施，可以使更大的QM区域被计算和更准确的光谱特征，包括非谐波振动效应。重要的是，我们将计算建模与实验结果相结合的方法将普遍适用于复杂系统中的任何化学过程，包括其他工业催化剂和生物分子。

项目成果

Bulk and Surface Contributions to Ionisation Potentials of Metal Oxides.

体相和表面对金属氧化物电离势的贡献。

• DOI: 10.1002/anie.202308411
• 发表时间: 2023
• 期刊: Angewandte Chemie (International ed. in English)
• 作者: Zhang X

Influence of Solvent on Selective Catalytic Reduction of Nitrogen Oxides with Ammonia over Cu-CHA Zeolite.

• DOI: 10.1021/jacs.2c09823
• 发表时间: 2023-01-11
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Nasir, Jamal Abdul;Guan, Jingcheng;Keal, Thomas W.;Desmoutier, Alec W.;Lu, You;Beale, Andrew M.;Catlow, C. Richard A.;Sokol, Alexey A.
• 通讯作者: Sokol, Alexey A.

Computational infrared and Raman spectra by hybrid QM/MM techniques: a study on molecular and catalytic material systems.

• DOI: 10.1098/rsta.2022.0234
• 发表时间: 2023-07-10
• 期刊: PHILOSOPHICAL TRANSACTIONS OF THE ROYAL SOCIETY A-MATHEMATICAL PHYSICAL AND ENGINEERING SCIENCES
• 影响因子: 5
• 作者: Guan, Jingcheng;Lu, You;Sen, Kakali;Nasir, Jamal Abdul;Desmoutier, Alec W. W.;Hou, Qing;Zhang, Xingfan;Logsdail, Andrew J. J.;Dutta, Gargi;Beale, Andrew M. M.;Strange, Richard W. W.;Yong, Chin;Sherwood, Paul;Senn, Hans M. M.;Catlow, C. Richard A.;Keal, Thomas W. W.;Sokol, Alexey A. A.
• 通讯作者: Sokol, Alexey A. A.

The Interplay of Interstitial and Substitutional Copper in Zinc Oxide.

• DOI: 10.3389/fchem.2021.780935
• 发表时间: 2021
• 期刊: Frontiers in chemistry
• 影响因子: 5.5
• 作者: Hou Q;Buckeridge J;Walsh A;Xie Z;Lu Y;Keal TW;Guan J;Woodley SM;Catlow CRA;Sokol AA
• 通讯作者: Sokol AA

Overcoming the compensation of acceptors in GaN:Mg by defect complex formation

通过形成缺陷复合物克服 GaN:Mg 中受主的补偿

• DOI: 10.1063/5.0148858
• 发表时间: 2023
• 期刊: APL Materials
• 影响因子: 6.1
• 作者: Xie Z