Nadeema Ayasha, Kashyap Varchaswal, Gururaj Rakshitha, Kurungot Sreekumar
Physical and Materials Chemistry Division , CSIR-National Chemical Laboratory , Pune 411008 , India.
Academy of Scientific and Innovative Research (AcSIR) , New Delhi 110001 , India.
ACS Appl Mater Interfaces. 2019 Jul 24;11(29):25917-25927. doi: 10.1021/acsami.9b06545. Epub 2019 Jul 11.
Substituting the energy-uphill water oxidation half-cell with readily oxidizable urea-rich urine, a ground-breaking bridge is constructed, combining the energy-efficient hydrogen generation and environmental protection. Hence, designing a robust multifunctional electrocatalyst is desirable for widespread implementation of this waste to fuel technology. In this context, here, we report a simple tuning of the electrocatalytically favorable characteristics of NiCo-layered double hydroxide by introducing [MoS] in its interlayer space. The [MoS] insertion as well as its effect on the electronic structure tuning is thoroughly studied via X-ray photoelectron spectroscopy in combination with electrochemical analysis. This insertion induces overall electronic structure tuning of the hydroxide layer in such a way that the designed catalyst exhibited favorable kinetics toward all the required reactions of hydrogen generation. This is why our homemade catalyst, when utilized both as a cathode and anode to fabricate a urea electrolyzer, required a mere ∼1.37 V cell potential to generate sufficient H by reaching the benchmark 10 mA cm in 1 M KOH/0.33 M urea along with long-lasting catalytic efficiency. Other indispensable reason of selecting [MoS] is its high-valent nature making the catalyst highly selective and insensitive to common catalyst-poisoning toxins of urine. This is experimentally supported by performing the real urine electrolysis, where the nanospike-covered Ni foam-based catalyst showed a performance similar to that of synthetic urea, offering its industrial value. Other intuition of selecting [MoS] was to provide a ligand-based mechanism for hydrogen evolution half-cell [hydrogen evolution reaction (HER)] to preclude the HER-competing oxygen reduction. Another crucial point of our work is its potential to avoid the mixing of two explosive product gases, that is, H and O.
用易于氧化的富含尿素的尿液替代能量上坡的水氧化半电池,构建了一座开创性的桥梁,将高效的氢气生成与环境保护结合起来。因此,设计一种强大的多功能电催化剂对于这种废物转化为燃料技术的广泛应用是很有必要的。在这种背景下,我们在此报告通过在其层间空间引入[MoS]来简单调节镍钴层状双氢氧化物的电催化有利特性。通过结合电化学分析的X射线光电子能谱对[MoS]的插入及其对电子结构调节的影响进行了深入研究。这种插入以这样一种方式诱导氢氧化物层的整体电子结构调节,即所设计的催化剂对氢气生成所需的所有反应都表现出有利的动力学。这就是为什么我们自制的催化剂在用作阴极和阳极来制造尿素电解槽时,在1 M KOH/0.33 M尿素中达到基准10 mA cm时仅需约1.37 V的电池电位就能产生足够的氢气,同时具有持久的催化效率。选择[MoS]的另一个不可或缺的原因是其高价性质使催化剂具有高选择性且对尿液中常见的催化剂中毒毒素不敏感。通过进行实际尿液电解得到了实验支持,其中基于纳米尖峰覆盖的泡沫镍的催化剂表现出与合成尿素相似的性能,展现了其工业价值。选择[MoS]的另一个直观原因是为析氢半电池[析氢反应(HER)]提供一种基于配体的机制,以排除与HER竞争的氧还原。我们工作的另一个关键点是其有潜力避免两种易爆产物气体,即氢气和氧气的混合。