Non Noble Metal Catalysts For Paired Electrocatalysis Of Furfural

Caused by the over-consumption of fossil fuels,the issues of environment pollution has become more and more seirous and limited to the further development of human society.Therefore,the renewable green fuels and the relavant clean technologies with high profits and low pollution have gained huge attentions.Biomass and its derivatives,which are one kinds of the most common renewable natural carbon source,have been widely studied due to its advantages,such as abundant reserves,green and clean products.It is of great significance to achieve high value-added conversion of biomass and its derivatives through rational design.Furfural,as a classic platform chemical,is a key raw material for producing series of biomass-based chemicals includingfurfuryl alcohol,furfuric acid and other high value-added chemicals,which has been widely used in the fields of fine chemicals and polymer industry.Moreover,the electrocatalytic conversion of biomass can be achieved in a mild,pollution-free condition and the operating parameters are controllable.However,the conventional electrocatalysis only focuses the half reaction at single electrode in the electrolytic system,resulting in the waste of electricity energy in the electrolytic process.To increase the profits and electricity utilization of electrocatalytic systems,the paired electrocatalysis which can integrate cathode and anode catalytic reactions has been proposed and designed.In this work,we coupled the furfural electrochemical reduction and oxidation at one electrocatalytic system and achieved the simultaneous generation of furfural alcohol and acid at cathode and anode,respectively.The main research has been described in brief as follows:(1)Cu NAs/Cu foil catalysts were prepared by a two-step method,and the properties such as micromorphology,chemical composition,and atomic valence states were analyzed.The results in situ Raman characterization has prove that Cu~0 is the active site of Cu NAs catalyst in the electrocatalytic hydrogenation process.The mechanism of furfural electrocatalytic hydrogenation was investigated by quasi in situ EPR and in situ infrared test methods.According to quantitative analysis by NMR and HPLC,the selectivity,conversion,and FE of Cu NAs catalysts can reach 92.0%,99.5%,and 96.1%,respectively.The Cu NAs/Cu foil catalyst also has excellent electrocatalytic performance for a series of furan ring and benzene ring unsaturated chemicals,showing excellent applicability.The performance of furfural electrocatalytic reduction of Cu obtained by different methods reducing Cu O has also been investigated.In addition,by using Cu NAs and Cu O NAs as catalysts in cathode and anode,respectively,a co-electrolysis system which can generate furfuryl alcohol and furoic acid simultaneously has been assembled,and exhibits good electrocatalytic performance and low electricity consumption.The system has(2)The Ni MOF nanosheet catalyst supported by nickel foam has been prepared by hydrothermal method and electrochemical oxidation method,and how different ligands can influence the geometry structure and electrochemical performance of the catalyst during hydrothermal process has been explored.The experimental results show that the application(addition)of N,N-dimethylpropanamide(DMP)in the hydrothermal process can improve the REDOX pair coverage rate on the surface of Ni MOF catalyst,and thus electrochemical performance of Ni MOF catalyst has improved.From the quantitative analysis characterized by NMR and HPLC,Ni MOF(DMP)shows the highest electrochemical performance,including the conversion rate,selectivity and Faraday efficiency of 92.5%,97.3%and 93.5%,respectively,for furoic acid production.In addition,Ni MOF(DMP)catalyst exhibits good electrochemical stability.