Manifesto on the Thermochemistry of Nanoscale Redox Reactions for Energy Conversion
Manifesto on the Thermochemistry of Nanoscale Redox Reactions for Energy Conversion
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DOI：
10.1021/acsenergylett.9b00019
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发表时间：
2019-04-01
影响因子：
22
通讯作者：
Mayer, James M.
中科院分区：
文献类型：
--
作者：
Peper, Jennifer L.;Mayer, James M.
使用纳米级材料进行能量转换的进展将依赖于对反应热化学的清晰理解。虽然带边和费米能量可以是块体材料的严格热力学描述符，但我们在此表明它们在纳米级系统中的应用是有问题的。 1000 个原子的纳米粒子或催化剂/电极上的局部表面位点的一个电子的变化会导致系统的显着核重组。电子转移通常与溶剂重组和/或离子转移相结合，包括离子嵌入、表面结合和周围双层内的移动。这些影响可能很大（即使对于某些散装材料也是如此）。然而，通常使用的费米和能带能量不包括核重组或阳离子耦合的能量。纳米级电荷转移热力学的综合方法必须明确考虑这些效应，以便更全面地理解和更好地控制纳米级氧化还原反应性。
Advancements in the use of nanoscale materials for energy conversions will rely on a clear understanding of reaction thermochemistry. While band edge and Fermi energies can be rigorous thermodynamic descriptors of bulk materials, we show here that their application to nanoscale systems is problematic. A change of one electron at a 1000 atom nanoparticle or a localized surface site on a catalyst/electrode causes significant nuclear reorganization of the system. Electron transfer is often coupled with solvent reorganization and/or with the transfer of ions, including ion intercalation, surface binding, and movement within the surrounding double layer. These effects can be significant (even for some bulk materials). However, Fermi and band energies, as typically used, do not include the energetics of nuclear reorganizations or cation coupling. A comprehensive approach to nanoscale charge transfer thermodynamics must explicitly consider these effects in order to have a more complete understanding and greater control of nanoscale redox reactivity.