Complete Protection of O2-Sensitive Catalysts in Thin Films
Complete Protection of O2-Sensitive Catalysts in Thin Films
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DOI：
10.1021/jacs.9b06790
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发表时间：
2019-10-23
影响因子：
15
通讯作者：
Plumere, Nicolas
中科院分区：
文献类型：
--
作者：
Li, Huaiguang;Buesen, Darren;Plumere, Nicolas
涉及二氢的能量转换方案在满足可持续能源需求方面具有巨大潜力，但如果没有降低稀有金属催化剂成本以及生物和生物替代品的O-2不稳定性的解决方案，就无法广泛实施。最近，氧化还原聚合物的厚膜（>100 μ m）显示出防止O-2催化剂损坏，但也导致不必要的催化剂负载和质量传递限制。在这里，我们应用新型的均匀薄膜（低至3 μ m），提供保护，从O-2，同时实现高效的催化剂利用率。我们的经验数据解释了建模，表明耐O-2失活可以获得非限制性的时间段时，达到催化剂利用率和电流生成的最佳厚度，即使使用高度脆弱的催化剂，如氢化酶。我们表明，不同的保护机制取决于矩阵的尺寸和固有的催化剂性能，可以整合在一起协同实现稳定的H-2氧化电流在O-2的存在下，可能使过多的实际应用生物启发催化剂在苛刻的氧化条件下。
Energy conversion schemes involving dihydrogen hold great potential for meeting sustainable energy needs, but widespread implementation cannot proceed without solutions that mitigate the cost of rare metal catalysts and the O-2 instability of biological and bioinspired replacements. Recently, thick films (>100 mu m) of redox polymers were shown to prevent O-2 catalyst damage but also resulted in unnecessary catalyst load and mass transport limitations. Here we apply novel homogeneous thin films (down to 3 mu m) that provide protection from O-2 while achieving highly efficient catalyst utilization. Our empirical data are explained by modeling, demonstrating that resistance to O-2 inactivation can be obtained for nonlimiting periods of time when the optimal thickness for catalyst utilization and current generation is achieved, even when using highly fragile catalysts such as the enzyme hydrogenase. We show that different protection mechanisms operate depending on the matrix dimensions and the intrinsic catalyst properties and can be integrated together synergistically to achieve stable H-2 oxidation currents in the presence of O-2, potentially enabling a plethora of practical applications for bioinspired catalysts under harsh oxidative conditions.