热载流子与光热等离子体太阳能化学的基本极限
Fundamental limits of hot-carrier and photothermal plasmonic solar chemistry
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中文总结 AI 辅助
该研究构建通道分辨详细平衡理论，明确热载流子与光热等离子体太阳能化学的效率极限，给出相关标度关系与基准，区分产物形成与净太阳能转换。
中文摘要 AI 辅助
等离子体催化剂通过直接的金属-吸附物激发、非平衡热载流子以及光热加热来转化太阳光，然而这些转化通道缺乏类似肖克利-奎伊瑟（Shockley-Queisser, SQ）极限的通用效率极限。本文针对等离子体太阳能化学构建了通道分辨的详细平衡理论，该理论要求吸收功率的排他性分配、微观可逆性、非负熵产生、电磁被动性和因果性，且所有波长和工作状态共享同一物理纳米结构。简化的紧密耦合循环遵循化学二极管定律，具有闭式的停滞和最大功率自由能；其恢复了33.68%的单阈值辐射极限，以及1.23 eV化学负载下30.58%的理想单结水分解极限，而福勒（Fowler）热载流子核将极限降至8.53%。有限单结构基准测试表明，独立波长优化对共享几何性能的高估幅度为6.6%至33.8%，跨频率相关性使半正定上界收紧21%至56%。精确的多电子网络给出了通用的到达-存储准则和低通量标度关系Jₙ∝gⁿτⁿ⁻¹。以源条件化的金/ p型氮化镓为案例研究，结合完整的偏压与分离 ledger，区分了增强的产物形成与净太阳能转换；所得框架为热载流子与光热等离子体化学提供了热力学闭合的基准。
英文摘要
Plasmonic catalysts convert sunlight through direct metal--adsorbate excitation, nonequilibrium hot carriers and photothermal heating, yet these channels lack a common efficiency limit analogous to the Shockley-Queisser (SQ) limit. Here, we formulate a channel-resolved detailed-balance theory for plasmonic solar chemistry. The theory enforces exclusive partition of absorbed power, microscopic reversibility, non-negative entropy production, electromagnetic passivity and causality, and one physical nanostructure shared by all wavelengths and operating states. A reduced tightly coupled cycle obeys a chemical diode law with closed-form stall and maximum-power free energies. It recovers a 33.68% single-threshold radiative limit and the 30.58% ideal single-junction water-splitting limit at a 1.23-eV chemical load, whereas a Fowler hot-carrier kernel lowers the limit to 8.53%. Finite one-structure benchmarks show that independent wavelength optimization overestimates shared-geometry performance by 6.6-33.8%, while cross-frequency correlations tighten semidefinite upper bounds by 21-56%. An exact multi-electron network yields a universal arrival-storage criterion and the low-flux scaling J_n\sim g^nτ^{n-1}. A source-conditioned gold/p-type gallium nitride case study and a bias- and separation-complete ledger then distinguish enhanced product formation from net solar-energy conversion. The resulting framework provides a thermodynamically closed benchmark for hot-carrier and photothermal plasmonic chemistry.
