Controlled Electrochemical Synthesis Of Metal-Organic Framework Materials

Metal-organic framework(MOF)materials were a class of porous crystalline materials based on coordination interactions between metal cations and organic ligands.MOFs are attractive to a myriad of applications due to their large surface areas,regular pore sizes,and tailorable surface chemistry,such as gas adsorption/separation,optoelectronic devices,sensor and energy storage areas.At present,there are many methods for preparing MOF,such as solvothermal method,liquid phase epitaxy and electrochemical method.Among these synthesis methods for MOF materials,electrochemical strategy is appealing due to its technological flexibility,scalable preparation,and industrial production potential.More importantly,its interfacial reaction nature greatly facilitates the direct production of MOFs as films on a substrate.Therefore,electrochemical method has received extensive attention.However,there are few reports on the preparation of Cu,Co,Ni based MOFs by the cathodic reduction method because of the low reduction potential of ions,which are easily plated on the cathode during the synthesis.Herein,we explored the electrochemically cathodic synthesis of Cu,Co,Ni with BTC,BDC,and successfully prepared Cu-BTC,Co-BDC,Ni-BDC without metal element.Besides,we regulated the mesoscopic structure of MOF materials such as film thickness through the control of reaction parameters.The effective adjustment for the mesoscopic structure(specific orientation,uniform and controllable film thickness,adjustable pore structure,etc.)can greatly improve the performance of MOF materials.And for that,we use the electrochemical method successfully prepared ZIF-8 with ordered macro-pore structure,and realized two-dimensional controlled selective growth of ZIF-8 on heterogeneous substrates.The specific research content is divided into the following three parts:(1)Investigate the feasibility of reaction between cuprous oxide and BTC ligands to obtain Cu-BTC,study the growth kinetics of Cu-BTC;besides,study the feasibility on the reaction of metal cobalt and nickel with terephthalic acid by electrochemical cathodic deposition method.(2)Through the combination of template method and electrochemical synthesis method,adjusting the relevant experimental parameters to construct MOFs with highly ordered macro-pore structure,and maintain its intact crystal structure,then explore its gas sensing performance.(3)Explore suitable materials to construct heterogeneous substrates,and through controlling the ORR reaction during the synthesis process to investigate whether the MOF materials can be controlled and selectively grown on heterogeneous substrates.