Jordan Jack W, Cameron Jamie M, Lowe Grace A, Rance Graham A, Fung Kayleigh L Y, Johnson Lee R, Walsh Darren A, Khlobystov Andrei N, Newton Graham N
Nottingham Applied Materials and Interfaces (NAMI) Group, GSK Carbon Neutral Laboratories for Sustainable Chemistry, University of Nottingham, Nottingham, NG7 2TU, UK.
Nanoscale and Microscale Research Centre, University of Nottingham, Nottingham, NG7 2RD, UK.
Angew Chem Int Ed Engl. 2022 Feb 14;61(8):e202115619. doi: 10.1002/anie.202115619. Epub 2022 Jan 3.
We describe the preparation of hybrid redox materials based on polyoxomolybdates encapsulated within single-walled carbon nanotubes (SWNTs). Polyoxomolybdates readily oxidize SWNTs under ambient conditions in solution, and here we study their charge-transfer interactions with SWNTs to provide detailed mechanistic insights into the redox-driven encapsulation of these and similar nanoclusters. We are able to correlate the relative redox potentials of the encapsulated clusters with the level of SWNT oxidation in the resultant hybrid materials and use this to show that precise redox tuning is a necessary requirement for successful encapsulation. The host-guest redox materials described here exhibit exceptional electrochemical stability, retaining up to 86 % of their charge capacity over 1000 oxidation/reduction cycles, despite the typical lability and solution-phase electrochemical instability of the polyoxomolybdates we have explored. Our findings illustrate the broad applicability of the redox-driven encapsulation approach to the design and fabrication of tunable, highly conductive, ultra-stable nanoconfined energy materials.
我们描述了基于包裹在单壁碳纳米管（SWNTs）内的多金属氧酸盐的混合氧化还原材料的制备。在溶液中的环境条件下，多金属氧酸盐很容易氧化SWNTs，在此我们研究它们与SWNTs的电荷转移相互作用，以深入了解这些及类似纳米团簇的氧化还原驱动封装的详细机理。我们能够将封装团簇的相对氧化还原电位与所得混合材料中SWNT的氧化水平相关联，并以此表明精确的氧化还原调节是成功封装的必要条件。尽管我们所研究的多金属氧酸盐具有典型的不稳定性和溶液相电化学不稳定性，但这里描述的主客体氧化还原材料表现出卓越的电化学稳定性，在1000次氧化/还原循环中保留了高达86%的电荷容量。我们的研究结果表明，氧化还原驱动封装方法在可调谐、高导电性、超稳定纳米受限能量材料的设计和制造方面具有广泛的适用性。
