SusChEM: Energies of Adsorbed Catalytic Intermediates on Transition Metal Surfaces: Experimental Benchmarks for Computational Catalysis Research

SusChEM：过渡金属表面吸附催化中间体的能量：计算催化研究的实验基准

• 批准号: 1665077
• 负责人: Charles Campbell
• 金额: $ 51万
• 依托单位: University of Washington
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2017
• 资助国家: 美国
• 起止时间: 2017-07-01 至 2020-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1665077&HistoricalAwards=false
• 关键词: SusChEM; Energies; Adsorbed; Catalytic; Intermediates

Catalysts are chemicals that provide more efficient and selective pathways for desirable chemical reactions. Transition metal catalysts are particularly useful in the production of bulk chemicals and fuels, and for cleaner fuel combustion and pollution cleanup. For these solid catalysts, metals at the catalyst surface bind the reacting chemicals with just the right strength (or "bond energy") to enable their chemical conversion to the desired products. Too tightly bound, and the product will not desorb but will remain attached to the catalyst surface. Too weakly bound and the reactant will not adsorb, and cannot react catalytically with it. Improving the energetics of such catalysts is essential for producing and using chemicals and fuels with higher energy efficiency and less pollution, as needed for sustainable living into the future. The key to improving the catalysts is to find materials whose surfaces bind the reacting chemicals with the optimum bond energies. In principle, this can be achieved by solving the equations of quantum mechanics (a branch of physics) with computers. Unfortunately, the math is very difficult, so mathematical approximations must be made for even the fastest computers to solve the equations in reasonable times. Experimental measurements of some of the bond energies are needed to compare to the computer results, to assess whether these approximations lead to incorrect bond energies. In this project, Dr. Charles T. Campbell is measuring bond energies for selected chemicals bound to transition metal surfaces, carefully chosen to enable development of new quantum mechanical methods for more accurately predicting such energies, and to improve the basic understanding of the catalyst's action. Improving the energy accuracy of such fast computations is transformative in the field of heterogeneous catalysis, enabling greater reliability in computer-based predictions of better catalyst materials. This research also provides strong interdisciplinary, research-integrated education for numerous young students, scientists and engineers, who get hands-on experience with state-of-the-art measurement instrumentation and its design. Dr. Campbell is involved in extensive outreach to the broader community, through his frequent public lectures, numerous editorships and advisory board memberships, and service to university and external science education initiatives.Late transition metal catalysts and electocatalysts are used in the production of bulk chemicals and fuels, for cleaner fuel combustion and for pollution cleanup. Improving such catalysts is essential for producing and using chemicals and fuels with higher energy efficiency and less pollution, as needed for sustainable living. With funding from the Chemical Catalysis Program of the Chemistry Division, Dr. Charles T. Campbell of the University of Washington is measuring the energetics of selected elementary chemical reactions occurring on late transition metal surfaces, carefully chosen to enable development of new theoretical methods for more accurately predicting such energies. This, in turn, improves the basic understanding of catalytic mechanisms, and facilitates the design of better catalysts. Dr. Campbell's calorimetric measurements, which cannot be performed with the same precision elsewhere in the world, are broadening the database of reliable experimental energies of adsorbed catalytic intermediates that can be used by theoreticians as benchmarks to guide development of computational methods with improved accuracy for calculating the energetics of chemical reactions at late transition metal surfaces. While density functional theory (DFT) has been extremely successful in catalysis research, prior results proved that the mean absolute errors in the energies of adsorbed intermediates from DFT exceeds 20 kJ/mol. The experimental database being developed here greatly facilitates ongoing efforts by the theoretical community to improve the energy accuracy of such fast computational methods, while also clarifying the energetic basis for structure-reactivity correlations in transition metal catalysis. These improvements are transformative for catalysis research, enabling greater reliability in computational prediction of reaction rates and mechanisms, and higher success rates in predicting better catalyst and electrocatalyst materials that are essential for sustainable living. This research also provides strong interdisciplinary, research-integrated education for numerous young science and engineering students and postdoctoral researchers, who get hands-on experience with state-of-the-art measurement instrumentation and its design. In addition to mentoring these young people, Dr. Campbell is involved in extensive outreach to the broader community, through his frequent public lectures, numerous editorships and advisory board memberships, and service to university and external science education initiatives.

催化剂是为所需化学反应提供更有效和选择性途径的化学品。 过渡金属催化剂在大宗化学品和燃料的生产以及清洁燃料燃烧和污染清除方面特别有用。对于这些固体催化剂，催化剂表面的金属以适当的强度（或“键能”）结合反应化学物质，使其化学转化为所需的产物。 结合太紧密，产物不会解吸，而是仍附着在催化剂表面。 结合太弱，反应物不会吸附，并且不能与其发生催化反应。 提高此类催化剂的能量对于生产和使用具有更高能源效率和更少污染的化学品和燃料至关重要，这是未来可持续生活的需要。 改进催化剂的关键是找到其表面以最佳键能结合反应化学物质的材料。 原则上，这可以通过用计算机求解量子力学（物理学的一个分支）方程来实现。 不幸的是，数学非常困难，因此即使是最快的计算机也必须进行数学近似才能在合理的时间内求解方程。 需要对一些键能进行实验测量，以与计算机结果进行比较，以评估这些近似值是否会导致不正确的键能。 在该项目中，Charles T. Campbell 博士正在测量与过渡金属表面结合的选定化学物质的键能，这些化学物质经过精心挑选，旨在开发新的量子力学方法，以更准确地预测此类能量，并提高对催化剂作用的基本了解。提高这种快速计算的能量精度在多相催化领域具有变革性，使基于计算机的更好催化剂材料的预测具有更高的可靠性。这项研究还为众多年轻学生、科学家和工程师提供了强大的跨学科、研究综合教育，让他们获得最先进的测量仪器及其设计的实践经验。 坎贝尔博士通过频繁的公开演讲、担任众多编辑和顾问委员会成员，以及为大学和外部科学教育活动提供服务，广泛参与了更广泛的社区活动。后过渡金属催化剂和电催化剂用于大宗化学品的生产和燃料，用于更清洁的燃料燃烧和污染清除。改进此类催化剂对于生产和使用具有更高能源效率和更少污染的化学品和燃料至关重要，以满足可持续生活的需要。 在化学系化学催化项目的资助下，华盛顿大学的 Charles T. Campbell 博士正在测量发生在后过渡金属表面上的选定基本化学反应的能量学，这些化学反应经过精心挑选，以便能够开发更多新的理论方法。准确预测此类能量。 这反过来又提高了对催化机制的基本理解，并有助于设计更好的催化剂。坎贝尔博士的量热测量在世界其他地方无法以相同的精度进行，正在扩大吸附催化中间体的可靠实验能量数据库，理论家可以将其用作基准来指导计算方法的开发，提高计算的准确性后过渡金属表面化学反应的能量学。 虽然密度泛函理论 (DFT) 在催化研究中非常成功，但先前的结果证明 DFT 吸附中间体能量的平均绝对误差超过 20 kJ/mol。这里开发的实验数据库极大地促进了理论界不断努力提高这种快速计算方法的能量精度，同时也阐明了过渡金属催化中结构-反应性相关性的能量基础。这些改进对催化研究具有变革性，使反应速率和机制的计算预测更加可靠，并提高预测可持续生活所必需的更好催化剂和电催化剂材料的成功率。 这项研究还为众多年轻的理工科学生和博士后研究人员提供了强大的跨学科、研究综合教育，让他们获得最先进的测量仪器及其设计的实践经验。 除了指导这些年轻人之外，坎贝尔博士还通过频繁的公开讲座、担任众多编辑和顾问委员会成员以及为大学和外部科学教育计划提供服务，广泛参与更广泛的社区活动。

项目成果

Enhanced Bonding of Pentagon–Heptagon Defects in Graphene to Metal Surfaces: Insights from the Adsorption of Azulene and Naphthalene to Pt(111)

石墨烯中五边形-七边形缺陷与金属表面的增强结合：从甘菊环和萘对 Pt(111) 吸附的见解

• DOI: 10.1021/acs.chemmater.9b03744
• 发表时间: 2020-01-24
• 期刊: Chemistry of Materials
• 影响因子: 8.6
• 作者: Benedikt P. Klein;S. Harman;Lukas Ruppenthal;G. Ruehl;Samuel J Hall;S. Carey;Jan Herritsch;M. Schmid;R. Maurer;R. Tonner;C. Campbell;J. M. Gottfried
• 通讯作者: J. M. Gottfried

The kinetics of elementary thermal reactions in heterogeneous catalysis

多相催化中基元热反应的动力学

• DOI: 10.1038/s41570-019-0138-7
• 发表时间: 2019-12
• 期刊: Nature Reviews Chemistry
• 影响因子: 36.3
• 作者: Park, G. Barratt;Kitsopoulos, Theofanis N.;Borodin, Dmitriy;Golibrzuch, Kai;Neugebohren, Jannis;Auerbach, Daniel J.;Campbell, Charles T.;Wodtke, Alec M.
• 通讯作者: Wodtke, Alec M.

Velocity-resolved kinetics of site-specific carbon monoxide oxidation on platinum surfaces

铂表面特定位点一氧化碳氧化的速度分辨动力学

• DOI: 10.1038/s41586-018-0188-x
• 发表时间: 2018-06-01
• 期刊: Nature
• 影响因子: 64.8
• 作者: J. Neugebohren;D. Borodin;H. Hahn;Jan Altschäffel;A. K;ratsenka;ratsenka;D. Auerbach;C. Campbell;D. Schwarzer;D. Harding;A. Wodtke;T. Kitsopoulos
• 通讯作者: T. Kitsopoulos

Bond Energies of Adsorbed Intermediates to Metal Surfaces: Correlation with Hydrogen–Ligand and Hydrogen–Surface Bond Energies and Electronegativities

吸附中间体与金属表面的键能：与氢-配体和氢-表面键能和电负性的相关性

• DOI: 10.1002/anie.201811225
• 发表时间: 2018-11
• 期刊: Angewandte Chemie International Edition
• 作者: Carey, Spencer J.;Zhao, Wei;Campbell, Charles T.
• 通讯作者: Campbell, Charles T.

Origin of Thermal and Hyperthermal CO 2 from CO Oxidation on Pt Surfaces: The Role of Post-Transition-State Dynamics, Active Sites, and Chemisorbed CO 2

Pt 表面 CO 氧化产生的热和超热 CO 2 的起源：过渡态后动力学、活性位点和化学吸附 CO 2 的作用

• DOI: 10.1002/anie.201900565
• 发表时间: 2019-03
• 期刊: Angewandte Chemie International Edition
• 作者: Zhou, Linsen;Kandratsenka, Alexander;Campbell, Charles T.;Wodtke, Alec M.;Guo, Hua
• 通讯作者: Guo, Hua