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Mechanistic insight into deep holes from interband transitions in Palladium nanoparticle photocatalysts

ABSTRACT: Summary Utilizing hot electrons generated from localized surface plasmon resonance is of widespread interest in the photocatalysis of metallic nanoparticles. However, hot holes, especially generated from interband transitions, have not been fully explored for photocatalysis yet. In this study, a photocatalyzed Suzuki-Miyaura reaction using mesoporous Pd nanoparticle photocatalyst served as a model to study the role of hot holes. Quantum yields of the photocatalysts increase under shorter wavelength excitations and correlate to “deeper” energy of the holes from the Fermi level. This work suggests that deeper holes in the d-band catalyze the oxidative addition of aryl halide R-X onto Pd0 at the nanoparticles' surface to form R-PdII-X complex, thus accelerating the rate-determining step of the catalytic cycle. The hot electrons do not play a decisive role. In the future, catalytic mechanisms induced by deep holes should deserve as much attention as the well-known hot electron transfer mechanism. Graphical abstract Highlights • Comparison of quantum yield across different wavelengths• Interband transitions from shorter wavelength excitation offering deeper holes• Deeper holes with stronger oxidizing power for higher quantum yield Chemistry; Catalysis; Materials science

SUBMITTER: Lyu P

PROVIDER: S-EPMC8792079 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Major transitions in nature and human society are accompanied by a substantial change towards higher complexity in the core of the evolving system. New features are established, novel hierarchies emerge, new regulatory mechanisms are required and so on. An obvious way to achieve higher complexity is integration of autonomous elements into new organized systems whereby the previously independent units give up their autonomy at least in part. In this contribution, we reconsider the more than 40 years old hypercycle model and analyse it by the tools of stochastic chemical kinetics. An open system is implemented in the form of a flow reactor. The formation of new dynamically organized units through integration of competitors is identified with transcritical bifurcations. In the stochastic model, the fully organized state is quasi-stationary whereas the unorganized state corresponds to a population with natural selection. The stability of the organized state depends strongly on the number of individual subspecies, n, that have to be integrated: two and three classes of individuals, [Formula: see text] and [Formula: see text], readily form quasi-stationary states. The four-membered deterministic dynamical system, [Formula: see text], is stable but in the stochastic approach self-enhancing fluctuations drive it into extinction. In systems with five and more classes of individuals, [Formula: see text], the state of cooperation is unstable and the solutions of the deterministic ODEs exhibit large amplitude oscillations. In the stochastic system self-enhancing fluctuations lead to extinction as observed with [Formula: see text] Interestingly, cooperative systems in nature are commonly two-membered as shown by numerous examples of binary symbiosis. A few cases of symbiosis of three partners, called three-way symbiosis, have been found and were analysed within the past decade. Four-way symbiosis is rather rare but was reported to occur in fungus-growing ants. The model reported here can be used to illustrate the interplay between competition and cooperation whereby we obtain a hint on the role that resources play in major transitions. Abundance of resources seems to be an indispensable prerequisite of radical innovation that apparently needs substantial investments. Economists often claim that scarcity is driving innovation. Our model sheds some light on this apparent contradiction. In a nutshell, the answer is: scarcity drives optimization and increase in efficiency but abundance is required for radical novelty and the development of new features.This article is part of the themed issue 'The major synthetic evolutionary transitions'.

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Mechanistic insight into deep holes from interband transitions in Palladium nanoparticle photocatalysts

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