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

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”

作　　者：Zelong Qiao Run Jiang Jimmy Yun Dapeng Cao 乔泽龙;姜润;Jimmy Yun;曹达鹏(北京化工大学,有机无机复合材料国家重点实验室,中国北京100029;青岛国际院士港研究院,中国山东青岛266000;新南威尔士大学化学工程学院,澳大利亚新南威尔士州)

机构地区：[1]State Key Laboratory of Organic‐Inorganic Composites,Beijing University of Chemical Technology,Beijing 100029,China [2]Qingdao International Academician Park Research Institute,Qingdao 266000,Shandong,China [3]School of Chemical Engineering,The University of New South Wales,Sydney,NSW 2052,Australia

出　　处：《Chinese Journal of Catalysis》2024年第9期44-53,共10页催化学报（英文）

基　　金：国家重点研发计划(2019YFA0210300);国家自然科学基金(22372006).

摘　　要：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 2.5Å.In short,the BASED theory can be considered as a general principle to understand catalytic mechanism of intermediates on surfaces.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ScN_(4)~ZnN_(4))和金属氧化物表面(RuO_(2)(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^(*)、CH_(3)^(*)和NH_(2)^(*)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R^(2)分别为0.95和0.9

关 键 词：Surface chemistry Surface catalysis D-band center theory Bonding orbital Anti-bonding orbital 

分 类 号：O647[理学—物理化学]