非贵金属单原子催化剂的进展与展望（英文）

发布时间：2018-05-29 01:32

本文选题：单原子催化剂 + 非贵金属　；参考：《催化学报》2017年09期

【摘要】：由于良好的催化活性和稳定性,贵金属催化剂已经被广泛应用于各种异相催化反应中,但是贵金属的稀有性和高成本无法满足未来日益增长的催化需求.2011年,张涛课题组成功地制备了高效、稳定的铂单原子催化剂.高效的单原子催化剂利用单个活性位点作为催化活性中心,可能会成为连接同相催化和异相催化的桥梁.然而从经济适用的长远角度考虑,将非贵金属催化剂缩小到原子尺度是否也会展现出优良的催化活性;是否有潜力替代目前已被广泛应用的贵金属催化剂?虽然现阶段非贵金属催化剂的催化性能仍无法达到贵金属催化剂的标准,但是已有相关研究从理论和实验上报道了非贵金属单原子催化剂及其优异的性能表明了其在未来发展中极其重要,因而,可以预见这两个疑问的答案都是肯定的.单原子概念的出现不仅为提高贵金属的催化性能及成本的降低指明了方向,同时也为制备具有高催化活性、甚至可与贵金属催化剂相媲美的非贵金属催化剂提供了可能性.我们在上述背景下,阐述了对单原子的概念日益加深的机制认知,并从理论和实验上概述了非贵金属单原子催化剂近期的发展情况,指出了目前的在单原子催化剂领域需要解决的一些问题,最后,针对研究现状,我们对未来单原子的发展提出了相应的展望.单原子催化剂具有较高的表面能,因而,如何寻找合适的基体与单原子相互作用,进而,使基体材料像一只手一样稳固地"抓紧"单原子,因而,降低其高表面能则是发挥优良催化性能的基础.强金属基体相互作用(SMSI)不仅可以将单原子限制在基体表面,亦会影响整个催化过程.目前应用于单原子催化剂的基体种类很多,如金属氧化物、金属以及其他材料,而对SMSI认知则主要分两大类,一类是源自于基体表面的结构缺陷,另一类是源于其电子缺陷.从目前的发展状况来看SMSI机制仍有很多疑惑尚未解决,例如对电子转移影响的认知等.理论研究表明,在某些反应中非贵金属单原子展示出可替代贵金属的催化性质.比如,在一氧化碳优先反应(PROX)中,单原子钴和钛展示出的催化性能可与贵金属相媲美;理论计算同样证明单原子镍在一氧化碳还原中的催化活性比单原子铱优秀,甚至与单原子铂类似.大量的实验进展也报道了非贵金属单原子同样能在其他反应中展现出优异的性能,如氧析出反应(OER)、氢析出反应(HER)和氧还原反应(ORR).对于单原子催化剂,还有很多问题需要我们去解决,例如基体对于催化过程的具体影响、非贵金属的电子结构对于其催化性能的影响,以及单原子在基体上产生相互作用的位点等问题.纵然有许多问题需要更加深入的研究,但是单原子概念的出现,使得非贵金属催化剂材料取代传统贵金属催化剂成为了可能.
[Abstract]:Due to their good catalytic activity and stability, noble metal catalysts have been widely used in various heterogeneous catalytic reactions, but the rare and high cost of precious metals can not meet the increasing demand for catalysis in the future. High efficient and stable platinum monatomic catalysts were successfully prepared by Zhang Tao team. The highly efficient monoatomic catalyst uses a single active site as the catalytic active center, which may become the bridge between the same phase catalysis and heterogeneous catalysis. However, from the long-term perspective of economic application, whether the reduction of non-noble metal catalysts to atomic scale will also show good catalytic activity, and whether it has the potential to replace the precious metal catalysts that have been widely used at present? Although the catalytic performance of non-noble metal catalyst is still not up to the standard of noble metal catalyst, However, relevant studies have reported theoretically and experimentally that non-precious metal monatomic catalysts and their excellent properties show that they are extremely important in the future development. Therefore, the answer to these two questions can be predicted to be yes. The appearance of monatomic concept not only indicates the direction of improving the catalytic performance and cost reduction of noble metals, but also provides the possibility for the preparation of non-noble metal catalysts with high catalytic activity and even comparable with noble metal catalysts. Under the above background, we expound the increasing understanding of the mechanism of the concept of single atom, and summarize the recent development of non-noble metal monatomic catalysts, both theoretically and experimentally. Some problems that need to be solved in the field of monatomic catalysts are pointed out. Finally, in view of the present research situation, we put forward the corresponding prospects for the development of monatomic catalysts in the future. Monatomic catalysts have high surface energy, so how to find the appropriate matrix to interact with the single atom, so that the matrix material can "grasp" the single atom as firmly as a hand, so, The reduction of its high surface energy is the basis for its excellent catalytic performance. The strong metal matrix interaction (SMSI) can not only limit the single atom to the substrate surface, but also affect the whole catalytic process. At present, there are many kinds of monatomic catalysts, such as metal oxides, metals and other materials. The cognition of SMSI is mainly divided into two categories, one is the structural defects derived from the substrate surface, the other is the electronic defects. From the current development situation, there are still many doubts about the SMSI mechanism, such as the understanding of the effect of electron transfer. Theoretical studies show that in some reactions, the non-noble metal monoatom exhibits the catalytic properties of substituted noble metals. For example, in the carbon monoxide preferential reaction (Prox), monoatomic cobalt and titanium exhibit catalytic properties comparable to those of precious metals, and theoretical calculations also prove that monatomic nickel has better catalytic activity than monatomic iridium in carbon monoxide reduction. Even monatomic platinum is similar. A large number of experimental advances have also been reported that non-noble metal monatoms can also exhibit excellent properties in other reactions, such as oxygen precipitation reaction, hydrogen precipitation reaction and oxygen reduction reaction. For monatomic catalysts, there are still many problems to be solved, such as the specific effect of the matrix on the catalytic process, and the influence of the electronic structure of the non-noble metal on its catalytic performance. The interaction sites of monatomic atoms on the matrix are also discussed. Although there are many problems that need to be further studied, the concept of single atom makes it possible for non-precious metal catalyst materials to replace traditional noble metal catalysts.
【作者单位】：吉林大学汽车仿真与控制国家重点实验室和材料科学与工程学院;西班牙能源协作研究中心;西班牙巴斯克科学基金会;
【基金】：国家自然科学基金(51372095) 吉林大学学术带头人专项基金(419080500630)
【分类号】：O643.36

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