How dynamic surface restructuring impacts intra-particle catalytic cooperativity

被引:0
作者
Punia, Bhawakshi [1 ]
Chaudhury, Srabanti [1 ]
Kolomeisky, Anatoly [2 ,3 ]
机构
[1] Indian Inst Sci Educ & Res, Dept Chem, Dr Homi Bhabha Rd, Pune 411008, Maharashtra, India
[2] Rice Univ, Dept Chem, Dept Chem & Biomol Engn, Dept Phys & Astron, 6100 Main St, Houston, TX 77005 USA
[3] Rice Univ, Ctr Theoret Biol Phys, 6100 Main St, Houston, TX 77005 USA
关键词
SINGLE-MOLECULE NANOCATALYSIS; NANOPARTICLES; REVEALS;
D O I
10.1063/5.0239455
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Recent experiments indicated that nanoparticles (NPs) might efficiently catalyze multiple chemical reactions, frequently exhibiting new phenomena. One of those surprising observations is intra-particle catalytic cooperativity, when the reactions at one active site can stimulate the reactions at spatially distant sites. Theoretical explanations of these phenomena have been presented, pointing out the important role of charged hole dynamics. However, the crucial feature of nanoparticles that can undergo dynamic structural surface rearrangements, potentially affecting the catalytic properties, has not yet been accounted for. We present a theoretical study of the effect of dynamic restructuring in NPs on intra-particle catalytic cooperativity. It is done by extending the original static discrete-state stochastic framework that quantitatively evaluates the catalytic communications. The dynamic restructuring is modeled as stochastic transitions between states with different dynamic properties of charged holes. Our analysis reveals that the communication times always decrease with increasing rates of dynamic restructuring, while the communication lengths exhibit a dynamic behavior that depends on how dynamic fluctuations affect migration and death rates of charged holes. Computer simulations fully support theoretical predictions. These findings provide important insights into the microscopic mechanisms of catalysis on single NPs, suggesting specific routes to rationally design more efficient catalytic systems.
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页数:10
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