D带中心理论的反常现象缘何存在?一个用于表面化学的新理论——“BASED理论”

doi:10.1016/S1872-2067(24)60100-2

催化学报 ›› 2024, Vol. 64: 44-53.DOI: 10.1016/S1872-2067(24)60100-2

D带中心理论的反常现象缘何存在?一个用于表面化学的新理论——“BASED理论”

乔泽龙^a, 姜润^a, Jimmy Yun^b^,^c, 曹达鹏^a^,^*()

^a北京化工大学, 有机无机复合材料国家重点实验室, 北京 100029, 中国
^b青岛国际院士港研究院, 山东青岛266000, 中国
^c新南威尔士大学化学工程学院, 新南威尔士州, 澳大利亚

收稿日期:2024-05-09 接受日期:2024-06-24 出版日期:2024-09-18 发布日期:2024-09-19
通讯作者: * 电子信箱: caodp@mail.buct.edu.cn (曹达鹏).
基金资助:
国家重点研发计划(2019YFA0210300);国家自然科学基金(22372006)

Why the abnormal phenomena of D-band center theory exist? A new BASED theory for surface catalysis and chemistry

Zelong Qiao^a, Run Jiang^a, Jimmy Yun^b^,^c, Dapeng Cao^a^,^*()

^aState Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
^bQingdao International Academician Park Research Institute, Qingdao 266000, Shandong, China
^cSchool of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia

Received:2024-05-09 Accepted:2024-06-24 Online:2024-09-18 Published:2024-09-19
Contact: * E-mail: caodp@mail.buct.edu.cn (D. Cao).
Supported by:
National Key Research and Development Project(2019YFA0210300);National Natural Science Foundation of China(22372006)

摘要/Abstract

摘要：

自D带中心理论提出以来, 因其易于理解、使用简便且相对准确, 已被广泛应用于表面化学的研究中. 然而, 在实际应用中, 其反常现象却时常出现, 这促使研究者们重新审视D带中心理论在表面催化与化学领域中应用的局限性. 随着材料科学及合成技术的飞速发展, 在小型金属粒子体系和半导体材料体系(特别是单原子体系), D带中心理论的局限性愈发凸显, 导致了许多与其预期不符的结论. 鉴于D带中心理论原本是基于较大金属粒子体系构建的, 因此, 深入探究D带中心理论反常现象的根源, 并构建新的理论以解决这一问题具有重要意义.

本文通过分析D带中心理论的起源及其物理意义, 发现有两个原因导致其出现反常现象: 一是仅考虑了轨道能级位置而忽略了电子数所带来的影响; 二是只考虑了材料整体的电子性质, 忽略了表面上存在多种活性位点以及吸附方式的多样性. 此外, 对于已有的表征键强度的描述符——晶体轨道哈密顿布居(COHP)所衍生出来的ICOHP, 其仅考虑了电子数的影响, 而忽略了轨道能级位置的作用, 这也导致存在较大的误差. 因此, 我们认为同时考虑轨道能级位置与电子数才能更准确地表征键的强度. 由于成键轨道可以增强键的强度, 而反键轨道则会削弱, 所以成键轨道与反键轨道之间的差值应该是一个有效的用于预测吸附能强弱的描述符. 基于上述分析, 我们提出了一个成键和反键轨道稳定电子强度差(BASED)的新理论. 为了验证该理论的准确性, 构建了包括金属颗粒表面(Pt(111), Ni(111), Ag(111)和Cu(111))、单原子催化剂(SACs, 包括ScN₄~ZnN₄)和金属氧化物表面(RuO₂(001))在内的多种模型体系, 并计算了这些模型体系对H*、O*、OH*、OOH*、CH₃*和NH₂*中间体的吸附行为. 结果表明, BASED理论在预测吸附能和键长方面展现出极高的准确性(相关系数R²分别为0.95和0.94), 远超ICOHP及D带中心描述符. 为了方便研究者们使用BASED理论、并推动其在表面化学领域的发展, 我们开发了基于Python的BASED v1.0程序, 供学术界免费使用. 此外, 值得注意的是, 基于BASED理论, 观察到了吸附过程中的一个奇特现象——自旋过渡态(STS). 即在吸附过程中, 活性中心原子在特定距离(约2.5 Å)处会呈现出高自旋过渡态来提升其吸附能力, 但稳定性相对较低; 而在吸附过程结束后, 高自旋态有时会转化为更稳定的低自旋态(是否转化取决于高自旋态与低自旋态的相对能量). 自旋过渡态现象可以为理解表面催化机制提供新的视角, 有助于研究者更好的理解活性位的吸附行为.

总之, BASED理论为表面化学和催化领域提供了新的描述符, 使研究者可以通过电子结构更精确地分析表面化学中的吸附和反应行为. 此外, 自旋过渡态现象为理解表面催化过程提供了新的物理视角, 能有效促进研究者对表面催化与化学反应机制的理解.

关键词: 表面化学, 表面催化, D带中心理论, 成键轨道, 反键轨道

Abstract:

Since the D-band center theory was proposed, it has been widely used in the fields of surface chemistry by almost all researchers, due to its easy understanding, convenient operation and relative accuracy. However, with the continuous development of material systems and modification strategies, researchers have gradually found that D-band center theory is usually effective for large metal particle systems, but for small metal particle systems or semiconductors, such as single atom systems, the opposite conclusion to the D-band center theory is often obtained. To solve the issue above, here we propose a bonding and anti-bonding orbitals stable electron intensity difference (BASED) theory for surface chemistry. The newly-proposed BASED theory can not only successfully explain the abnormal phenomena of D-band center theory, but also exhibits a higher accuracy for prediction of adsorption energy and bond length of intermediates on active sites. Importantly, a new phenomenon of the spin transition state in the adsorption process is observed based on the BASED theory, where the active center atom usually yields an unstable high spin transition state to enhance its adsorption capability in the adsorption process of intermediates when their distance is about 2.5 Å. In short, the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.

Key words: Surface chemistry, Surface catalysis, D-band center theory, Bonding orbital, Anti-bonding orbital

乔泽龙, 姜润, Jimmy Yun, 曹达鹏. D带中心理论的反常现象缘何存在?一个用于表面化学的新理论——“BASED理论”[J]. 催化学报, 2024, 64: 44-53.

Zelong Qiao, Run Jiang, Jimmy Yun, Dapeng Cao. Why the abnormal phenomena of D-band center theory exist? A new BASED theory for surface catalysis and chemistry[J]. Chinese Journal of Catalysis, 2024, 64: 44-53.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60100-2

https://www.cjcatal.com/CN/Y2024/V64/I9/44

图/表 5

Fig. 1. Illustrations of D-band center theory and anti-D-band center phenomenon. (a) D-band center theory; (b) Anti-D-band center phenomenon.

Fig. 2. Illustrations of BASED theory. (a) Schematic diagram of molecular orbital conversion to BASED. (b?d) Schematic diagram of three different bonding and anti-bonding orbitals, where the anti-bonding orbitals gradually right shift until they become unoccupied orbitals.

Fig. 3. Adsorption illustrations of different surface models. (a) The O*, OH*, H*, CH3* and NH2* adsorption models of SAC, including all kinds of 3d transition metal SACs. (b) The O*, OH*, OOH* and H* adsorption models of expanded material surface models (Bulk models) after adsorption, including RuO2 (001), Pt (111), Ni (111), Ag (111), and Cu (111) bulk models.

Fig. 4. Theoretical calculation results from different methods. The relationship between adsorption energy of intermediates and εd, OH* (a), O* (b) and H* (c). (d) The red circle represents four types of SACs with anti-D-band center phenomenon. (e) Projected DOS (PDOS) diagram of all 3d metal SACs slab. (f) The relationship between -ICOHP and adsorption energy. The larger the -ICOHP, the stronger the adsorption capability. The relationship between Q and adsorption energy. The larger the Q, the stronger the adsorption capability. (g) The relationship between -ICOHP and bond length. (h) The relationship between Q and bond length.

Fig. 5. Illustrations of STS phenomenon. (a) Schematic diagram of active center atoms in low spin state. (b) Schematic diagram of active center atoms in high spin state. (c) Schematic diagram of active center atoms completing adsorption process. The relationship between magnetic moment of active center atoms and the distance between the adsorbent (H*, O* and OH*) and slab, based on FeN4 (d), CoN4 (e), NiN4 (f), where the gray arrow represents the trend of magnetic moment variation with height. The relationship between magnetic moment of active center atoms and Q, based on FeN4 (g), CoN4 (h), NiN4 (i). High value of Q represents strong adsorption capability of the active center atom. The gray arrow represents the trend of the adsorption capability indicator Q with respect to magnetic moment.

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D带中心理论的反常现象缘何存在?一个用于表面化学的新理论——“BASED理论”

Why the abnormal phenomena of D-band center theory exist? A new BASED theory for surface catalysis and chemistry

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