Su Minglei,Zhang Rong,Li Jingpeng,Jin Xiaobei,Zhang Xiaofeng,Qin Daochun
Bamboo, as a fast-grown forest resource, can be functionalized by metal–organic frameworks (MOFs) with various potential applications. However, the stability of MOFs immobilized on bamboo surface remains to be improved. In this work, MOF199, as known as HKUST-1, was in situ anchoring on moso bamboo via regulating pretreatment of bamboo and a green two-step synthesis route. The two-step synthesis route was completed under room temperature and both precursor solutions can be reused. The results indicated that, with the collaboration of delignification and carboxymethylation pretreatment of bamboo, a dense and well-dispersed MOF coating was successfully synthesized, the adhesion between MOF199 and bamboo surface was also improved. Besides, the quantity and size of MOF199 on bamboo can be tailored by tunning the carboxyl groups of pretreated bamboo and the concentration of copper nitrate solution. More importantly, results show that the formation of carboxyl-copper (II) complex served as nucleation sites for the growth of MOF199 crystals, which was essential to prepare uniform MOF layers. The growth of MOF199 endowed bamboo with good antibacterial activity against Escherichia coli . This method provides a facile and practical strategy for designing MOF coated woody materials. Graphic abstract
It remains a huge challenge to develop non precious electrocatalysts with high activity to substitute commercial Pt catalysts for hydrogen evolution reactions (HER). Here, the C-Cu-DI and C-Cu materials with the copper based nanoporous carbon structures were synthesized by carbonizing MOF199 and DI-MOF199. The composite structure and HER electrocatalytic properties of the C-Cu-DI and C-Cu materials are studied. The results show that C-Cu-DI and C-Cu samples exhibit good catalytic activity. And C-Cu-DI sample through the addition of Dimethyl imidazole(DI) in the DI-MOF199 precursor has higher electrocatalytic activity than the C-Cu sample. The superior catalytic activity is attributed to the special composite structure of nanoscale deposition particles on the framework with plenty of nano pores and nano copper and few copper oxidation particles distributed or wrapped into the amorphous porous carbon phase. The nano copper and few copper oxidation particles in the C-Cu and C-Cu-DI catalysts maybe provide the more effective catalytic activity sites. The C-Cu-DI composite with large size spherical hollow deposition particles has higher conductivity, better BET surface area and reasonable micro-meso-macro porous distribution, so the overpotentials at the current density of 1 mA cm −2 and 10 mA cm −2 are respectively 270 mV and 390 mV vs. RHE. Although the HER activity has a big gap with commercial platinum catalyst, this study can provide an important experimental exploration for the design of copper based non noble metal/nano porous carbon composite HER electrocatalyst.
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