人工光合作用中光生电荷的量子隧穿。

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY
Accounts of Chemical Research Pub Date : 2025-07-01 Epub Date: 2025-06-18 DOI:10.1021/acs.accounts.5c00295
Ying Wang, Shuowen Wang, Xianzhi Fu, Jinlin Long
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引用次数: 0

摘要

CO2和H2O的光催化转化为高价值的化学品或燃料为有效实现太阳能-化学能的转换和储存提供了重要途径;然而,总效率受到光生电荷空间分离的严重限制。光激发半导体粒子中电荷的寿命与界面氧化还原反应的速率完全不匹配,从而动态地锁定目标反应。为了最大限度地提高光生电荷在人工光合作用中的可用性,构建各种类型的异质结(包括Schottky, p-n和Z/ s方案)被广泛用于控制光生电荷向表面活性位点的定向迁移,从而进行光氧化还原催化。尽管如此,在由厚度小于1.0 nm的几个原子层组成的界面异质结上,最初分离的电荷不可避免地会重新组合,在那里库仑力仍然占主导地位,导致催化剂颗粒表面或界面上的电荷二次损失。如何消除电荷的库仑约束一直是光催化和太阳能转换领域中一个非常有趣的话题,但也是一个巨大的挑战。在这篇文章中,为了抑制最初分离的电荷的重组,我们引入了一种新的电荷隧道分离策略来设计有效的人工光系统用于CO2转化。在半导体和金属之间插入绝缘体,形成金属-绝缘体-半导体(MIS)结构,其中电荷供体和受体被几纳米厚度的绝缘层在空间上分开,完全不同于具有直接接触M/S界面的传统肖特基结。半导体单元的光激发产生大量的热电子和空穴,然后它们立即隧道到金属催化剂上,通过两个M/I和I/S界面和绝缘层进行氧化还原反应。隧穿分离在平均自由程的几阿秒内进行。这些隧穿电子或空穴被捕获、集中和定位在由金属单原子、纳米团簇(NCs)或纳米颗粒(NPs)组成的催化单元上,因此本报告的重点将放在三个方面:(1)了解人工光合作用光生电荷量子隧穿的物理基础;(2)巧妙设计包括光吸收剂、绝缘体、催化活性中心和界面在内的功能单元的化学成分和结构,以最大限度地提高隧穿概率;(3)构建mis型全太阳能驱动的人工光合系统。其中负责二氧化碳还原和水氧化的功能单元在空间上是分开的,以实现太阳能到化学能的有效转换。结果表明,光化学转化效率(ηSCC)为13.6%。这项工作为设计新型、高性能的光催化剂和光电极提供了指导,并为大规模生产太阳能燃料奠定了基础。最后,讨论了基于量子隧道的人工光合作用面临的挑战和前景。双向隧道增强人工叶片技术有望促进高效耐用的人工光系统的发展,能够将太阳能转化为燃料和化学品。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
Quantum Tunneling of Photogenerated Charges for Artificial Photosynthesis.

ConspectusPhotocatalytic conversion of CO2 and H2O to high-value chemicals or fuels provides a crucial pathway for efficiently achieving the conversion and storage of solar-to-chemical energy; however, the overall efficiency is severely restricted by the spatial separation of photogenerated charges. The lifetime of charges in a photoexcited semiconductor particle is mismatched utterly with the rate of interfacial redox reactions, locking kinetically the target reactions. To maximize the availability of photogenerated charges for artificial photosynthesis, constructing various types of heterojunctions including Schottky, p-n, and Z/S-scheme is widely used to manipulate the directional migration of photogenerated charges toward surface active sites, where photoredox catalysis proceeds. Even so, it is unavoidable for the recombination of initially separated charges at the interfacial heterojunctions composed of several atomic layers with less than 1.0 nm thickness, where the Coulomb force remains dominant, leading to the quadratic loss of charges on the surface or interface of catalyst particles. How to eliminate the Coulomb confinement for charges has been a highly interesting topic and yet a formidable challenge in the domain of photocatalysis and solar energy conversion.In this Account, aiming to suppress the recombination of initially separated charges, we introduced a novel strategy of charge tunneling separation to design efficient artificial photosystems for CO2 conversion. An insulator is inserted between the semiconductor and metal to form the metal-insulator-semiconductor (MIS) structure, where the charge donor and acceptor are spatially separated by the insulating layer with a thickness of a few nanometers, different completely from the conventional Schottky junction with a direct contact M/S interface. Photoexcitation of the semiconductor unit generates a large population of hot electrons and holes, and then they immediately tunnel to the metal catalyst for redox reactions across the two M/I and I/S interfaces and the insulating layer. The tunneling separation proceeds within a few attoseconds at a mean free path. These tunneled electrons or holes are trapped, concentrated, and localized on the catalytic units consisting of metallic single atoms, nanoclusters (NCs), or nanoparticles (NPs), and thus the emphasis of this Account will be put on three aspects: (1) understanding the physical fundamentals of quantum tunneling of photogenerated charges for artificial photosynthesis, (2) smartly designing the chemical components and structures of functional units including photoabsorbers, insulators, catalytic active centers and interfaces to maximize the tunneling probability, and (3) constructing a MIS-type all-solar-driven artificial photosynthetic system, where the functional units responsible for CO2 reduction and water oxidation are spatially segregated to enable efficient conversion of solar-to-chemical energy. As a result, a solar-to-chemical conversion efficiency (ηSCC) of 13.6% was achieved for the photosynthetic reaction. This work offers guidance for designing novel, high-performance photocatalysts and photoelectrodes and lays the foundation for producing solar fuels at a large scale. Finally, the challenges and outlook for quantum tunneling-based artificial photosynthesis are discussed. Bidirectional tunneling-enhanced artificial leaf technology is expected to facilitate the development of efficient and durable artificial photosystems capable of converting solar energy to fuels and chemicals.

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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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