Department of Chemistry and Biochemistry, Arizona State University , Tempe, Arizona 85287-1604, United States.
J Am Chem Soc. 2014 Jul 23;136(29):10198-201. doi: 10.1021/ja504282w. Epub 2014 Jul 10.
The utilization of solar energy requires an efficient means for its storage as chemical energy. In bioinspired artificial photosynthesis, light energy can be used to drive water oxidation, but catalysts that produce molecular oxygen from water are needed to avoid excessive driving potentials. In this paper, we demonstrate the utility of a novel complex utilizing earth-abundant Ni in combination with glycine as an efficient catalyst with a modest overpotential of 0.475 ± 0.005 V at a current density of 1 mA/cm(2) at pH 11. Catalysis requires the presence of the amine moiety with the glycine most likely coordinating the Ni in a 4:1 molar ratio. The production of molecular oxygen at a high potential is verified by measurement of the change in oxygen concentration, yielding a Faradaic efficiency of 60 ± 5%. The catalytic species is most likely a heterogeneous Ni-hydroxide formed by electrochemical oxidation. This Ni species can achieve a current density of 4 mA/cm(2) that persists for at least 10 h. Based upon the observed pH dependence of the current amplitude and oxidation/reduction peaks, the catalytic mechanism is an electron-proton coupled process.
太阳能的利用需要一种有效的方法将其储存为化学能。在仿生人工光合作用中,可以利用光能驱动水氧化,但需要催化剂将水转化为氧气,以避免过高的驱动电位。本文展示了一种新型配合物的应用,该配合物利用丰富的镍与甘氨酸结合,作为一种高效催化剂,在 pH 值为 11 时,电流密度为 1 mA/cm(2)时,过电势适中,为 0.475 ± 0.005 V。催化需要存在胺部分,甘氨酸最有可能以 4:1 的摩尔比与 Ni 配位。通过测量氧气浓度的变化来验证氧气的高电势生成,产率为 60 ± 5%。催化物种很可能是由电化学氧化形成的非均相 Ni 氢氧化物。这种 Ni 物种可以达到 4 mA/cm(2)的电流密度,并持续至少 10 小时。根据观察到的电流幅度和氧化/还原峰的 pH 值依赖性,催化机制是一个电子-质子偶联过程。