Electrochemical oxidation and reduction reactions are fundamental in various conversion and energy storage devices. Functional materials derived from MOFs have been considered promising as electrical catalysts for ORR, HER, and OER, which can be used in Zinc-air batteries and water electrolysis. Herein, we designed a novel approach to fabricating the ultrafine Co9S8 embedded nitrogen-doped hollow carbon nanocages ( Co9S8@N-HC). The method involved a process of sulfidation of cobalt-based metal–organic frameworks (ZIF67) and then coating them with polypyrrole (PPy). PPy has notable properties such as high electrical conductivity and abundant nitrogen content, rendering it highly promising for catalytic applications. The Co9S8@ N-HC catalyst was successfully synthesized via the carbonization of CoSx@ PPy. Remarkably, the Co9S8@ N-HC catalyst demonstrated exceptional electrocatalytic activity, requiring only low overpotentials of 285 mV and 201 mV at 10 mA cm‒ 2 for OER and HER, respectively, and exhibited high activity for ORR, with an onset potential ( Eonset) of 0.923 V and half-wave potential ( E1/2) of 0.879 V in alkaline media. The electrocatalytic efficiency displayed by Co9S8@ N-HC opens a new line of research on the synergistic effect of MOF-PPy materials on energy storage and conversion.
A series of ZIF-67-C-IL catalysts were prepared using ZIF-67 and 1-butyl-3-methylimidazolium bis[(trifluoromethyl)sulfonyl] imide ([ BMIM]NTf2) ionic liquid as precursors. The structure of the catalysts was characterized by XRD, TEM, SEM and XPS. The catalytic performance of the catalysts for the oxygen reduction reaction (ORR) was evaluated in a three-electrode system. The results confirmed that the high-temperature treatment of the precursors resulted in the formation of N, S codoped carbon-encapsulated Co9S8 nanoparticles. To create N, S co-doped carbon coated Co9S8 nanoparticle catalysts, ionic liquids are used as sulfur and nitrogen sources. The catalytic activity of ORR can be improved using N, S co-doped carbon to prevent the aggregation of Co9S8 nanoparticles. Graphitized and N, S co-doped carbon shells are optimal for achieving high activity stability. Optimal 600-ZIF-67-C(1:1.5)-30IL catalytic activity was observed for ORR. The half-wave potential of ORR was 0.88 V vs. RHE in 0.1 mol L− 1 KOH, with a limit current density of 4.70 mA cm− 2. Similar ORR electrocatalytic activity was observed between this catalyst and commercial Pt/C (20 wt%).
본 연구에서는 zeolitic imidazolate framework-9 (ZIF-9)을 합성하고 poly(ether-b-amide)-1657 (Pebax-1657) 내에 함량을 달리하여 Pebax/ZIF-9 혼합막을 제조한 다음 단일기체 (N2, CO2)를 투과하여 혼합막에 대한 기체 투과 특성을 조사하 였다. 순수 Pebax 막 내에 혼입되는 ZIF-9 함량이 증가함에 따라 N2 투과도는 점차 감소하고, CO2 투과도는 Pebax/ZIF-9 3 wt% 혼합막까지 증가하다가 그 이후의 함량에서는 감소하였다. 그리고 혼합막들 중 Pebax/ZIF-9 3 wt% 혼합막은 극성 기체 인 CO2에 대해 gate-opening 현상이 일어나면서 선택적으로 CO2를 받아들여 가장 높은 선택도 69.3을 보였다. 또한 CO2 투 과도와 CO2/N2 선택도가 모두 증가하여 Robeson upper-bound에 가장 근접하는 결과를 얻었다.