通过限域-热解策略可控合成双原子催化剂

doi:10.1016/S1872-2067(23)64436-5

摘要/Abstract

摘要：

双原子催化剂(DACs)是单原子催化剂(SACs)的升级版, 在保留SACs 100%原子利用效率等优点的同时, 其与支撑衬底间的相互作用更强, 活性中心的几何/电子结构更灵活可调, 双原子对之间具有独特的协同作用优势. 因此, DACs可以超越单原子位点反应性能理论极限, 成为更加理想的催化剂. 尽管DACs跻身最新的研究前沿, 但目前报道的可控合成DACs途径仍是基于制备SACs的方法, 包括成本高昂、适用性有限的原子层沉积法, 产物稳定性差的湿化学法和易发生不利团聚的高温热解法等, 这些方法都存在不可忽视的缺点. 因此, 迫切需要探索更高效巧妙且具有普适性的制备DACs方法.

本文对Niu等(J. Am. Chem. Soc., 2023, 145, 4819-4827)的工作进行了评述. 作者报道了一种普适性的基于封装-热解策略的合成方法, 并由此成功建立了一个涵盖同核和异核双金属位点的DACs库. 报道的合成途径可分为封装和热解两步, 其核心是将大环金属配合物(M¹M²L)包封到多孔金属-有机骨架材料(ZIF-8)的腔体中实现对最终DACs结构的介导. 精心设计的多功能Robson型大环配体提供了一个能够与大多数金属离子实现强配位的多功能配位平台, 使得该合成方法可以普遍适用于几乎所有广泛用于催化领域的过渡金属元素, 可兼容对多种同核/异核双金属位点组合的包封. 作为封装外壳的多孔ZIF-8框架内部容量有限, 对Robson型大环配合物前体具有空间限制作用, 从根本上抑制了后续高温热解处理过程中不利的热迁移和团聚趋势, 从而在很大程度上保持了同Robson型前体高度近似的双金属配位结构. 该工作所呈现出的可控合成的设计理念, 激励着研究者们拓宽创新方向来助力DACs未来的蓬勃发展. 相关研究表明, 脱金属化和碳腐蚀是降低耐久性的两个主要过程, 而铁基催化剂通过类芬顿反应产生的活性氧(ROS)可以进一步削弱稳定性. 然而, 研究发现Fe-Cu DAC在催化氧还原反应(ORR)时不是基于一般的类芬顿途径, 而是基于一种双电子还原过程, 经过该过程, 副产物H₂O₂可以高活性地被还原为H₂O而不是有害的ROS, 使得基本反应步骤可控. 此外, 作者结合理论计算研究进一步证实了上述有利途径的存在. 因此, Fe-Cu DAC表现突出的ORR催化性能和较好的稳定性, 在10000个电位循环后, ΔE_1/2仅为5 mV. 综上, 该文章报道的合成方法将启发人们解锁DACs在许多其他电化学反应中的未知反应途径, 从而极大释放DACs的催化潜力, 如析氧反应、CO₂还原反应、N₂还原反应等.
关键词:

关键词: 双原子催化剂, 多金属, 金属负载量, 异核, 反应途径

韩璟怡, 管景奇. 通过限域-热解策略可控合成双原子催化剂[J]. 催化学报, 2023, 49: 1-4.

Jingyi Han, Jingqi Guan. Controllable synthesis of dual-atom catalysts by a confinement-pyrolysis strategy[J]. Chinese Journal of Catalysis, 2023, 49: 1-4.

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Method	Principle	Advantage	Disadvantage	Ref.
Confinement- pyrolysis strategy	metal atoms are prevented from aggregating through the confined effect of the template	high metal loading and stability; high ratio of diatomic pair; even distribution of active sites; regulable diatomic coordination structure; universal applicability of metal elements	precursor requires careful design; size effect limitation	[4]
Typical high- temperature pyrolysis	high temperature energized breaking/forming chemical bonds to anchor atomic sites	mature technique; universal applicability of metal elements	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites; severe high temperature synthesis condition	[5]
Double solvent wet chemical method	substrates can trap metal atoms via the hydrophilic/hydrophobic properties of different solvents	simple synthesis procedure; mild experimental condition;	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites	[6]
ALD technique	the vapor precursors alternately pulse to form the deposition film, which is then chemically adsorbed on the substrate and via self-limiting reactions to form the atomic layer	adjustable parameters; even distribution of active sites; remarkable reproducibility	high cost; special requirements for metal precursors and substrates; limited applicability of metal elements; time-consuming	[2]
Mechanical ball-milling method	sever and reconstruct the chemical bonds of precursors by applying physical stress	potential for large-scale production; low cost; universal applicability of metal elements	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites	[7]
Electrochemical deposition method	metal atoms can be electrodeposited on electrodes via external current	adjustable applied electrochemical parameters	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites	[8]
Ultrashort thermal shock route	thermal shock wave with rapid energy input to obtain atomic sites	high metal loading; high ratio of diatomic pair; universal applicability of metal elements	harsh experimental conditions; high cost; not applicable on a large scale	[9]

Method	Principle	Advantage	Disadvantage	Ref.
Confinement- pyrolysis strategy	metal atoms are prevented from aggregating through the confined effect of the template	high metal loading and stability; high ratio of diatomic pair; even distribution of active sites; regulable diatomic coordination structure; universal applicability of metal elements	precursor requires careful design; size effect limitation	[4]
Typical high- temperature pyrolysis	high temperature energized breaking/forming chemical bonds to anchor atomic sites	mature technique; universal applicability of metal elements	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites; severe high temperature synthesis condition	[5]
Double solvent wet chemical method	substrates can trap metal atoms via the hydrophilic/hydrophobic properties of different solvents	simple synthesis procedure; mild experimental condition;	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites	[6]
ALD technique	the vapor precursors alternately pulse to form the deposition film, which is then chemically adsorbed on the substrate and via self-limiting reactions to form the atomic layer	adjustable parameters; even distribution of active sites; remarkable reproducibility	high cost; special requirements for metal precursors and substrates; limited applicability of metal elements; time-consuming	[2]
Mechanical ball-milling method	sever and reconstruct the chemical bonds of precursors by applying physical stress	potential for large-scale production; low cost; universal applicability of metal elements	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites	[7]
Electrochemical deposition method	metal atoms can be electrodeposited on electrodes via external current	adjustable applied electrochemical parameters	low metal loading; low ratio of diatomic pair; high aggregation probability; poor dispersion of active sites	[8]
Ultrashort thermal shock route	thermal shock wave with rapid energy input to obtain atomic sites	high metal loading; high ratio of diatomic pair; universal applicability of metal elements	harsh experimental conditions; high cost; not applicable on a large scale	[9]

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通过限域-热解策略可控合成双原子催化剂

Controllable synthesis of dual-atom catalysts by a confinement-pyrolysis strategy

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