Waag Friedrich, Gökce Bilal, Kalapu Chakrapani, Bendt Georg, Salamon Soma, Landers Joachim, Hagemann Ulrich, Heidelmann Markus, Schulz Stephan, Wende Heiko, Hartmann Nils, Behrens Malte, Barcikowski Stephan
University of Duisburg-Essen, Center for Nanointegration Duisburg-Essen (CENIDE), Duisburg, 47057, Germany.
University of Duisburg-Essen, Institute of Technical Chemistry I, Essen, 45141, Germany.
Sci Rep. 2017 Oct 13;7(1):13161. doi: 10.1038/s41598-017-13333-z.
Highly active, structurally disordered CoFeO/CoO electrocatalysts are synthesized by pulsed laser fragmentation in liquid (PLFL) of a commercial CoFeO powder dispersed in water. A partial transformation of the CoFeO educt to CoO is observed and proposed to be a thermal decomposition process induced by the picosecond pulsed laser irradiation. The overpotential in the OER in aqueous alkaline media at 10 mA cm is reduced by 23% compared to the educt down to 0.32 V with a Tafel slope of 71 mV dec. Importantly, the catalytic activity is systematically adjustable by the number of PLFL treatment cycles. The occurrence of thermal melting and decomposition during one PLFL cycle is verified by modelling the laser beam energy distribution within the irradiated colloid volume and comparing the by single particles absorbed part to threshold energies. Thermal decomposition leads to a massive reduction in particle size and crystal transformations towards crystalline CoO and amorphous CoFeO. Subsequently, thermal melting forms multi-phase spherical and network-like particles. Additionally, Fe-based layered double hydroxides at higher process cycle repetitions emerge as a byproduct. The results show that PLFL is a promising method that allows modification of the structural order in oxides and thus access to catalytically interesting materials.
通过对分散在水中的商用CoFeO粉末进行液体脉冲激光破碎(PLFL)合成了高活性、结构无序的CoFeO/CoO电催化剂。观察到CoFeO反应物部分转化为CoO,并认为这是由皮秒脉冲激光辐照引起的热分解过程。与反应物相比,在碱性水溶液介质中10 mA cm下的OER过电位降低了23%,降至0.32 V,塔菲尔斜率为71 mV dec。重要的是,催化活性可通过PLFL处理循环次数进行系统调节。通过对辐照胶体体积内的激光束能量分布进行建模,并将单个粒子吸收的部分与阈值能量进行比较,验证了在一个PLFL循环中热熔化和分解的发生。热分解导致粒径大幅减小,并向结晶CoO和非晶CoFeO发生晶体转变。随后,热熔化形成多相球形和网络状颗粒。此外,在较高的工艺循环重复次数下,铁基层状双氢氧化物作为副产物出现。结果表明,PLFL是一种很有前途的方法,可以改变氧化物中的结构有序性,从而获得具有催化活性的有趣材料。