Controllable Preparation And Electrocatalytic Applications Of Metal-organic Framework-based Nanomaterials

Metal-organic frameworks?MOFs?nanomaterials are ascendant in the field of electrocatalysis.Compared with other catalysts,MOFs nanomaterials have many advantages,which are derived from:?1?MOFs crystals are easy to design and construct.?2?MOFs crystal structures have open metal sites and contain specific functional heteroatoms.?3?MOFs crystals are easy to encapsulate the guest,and its lattice is easy to modify.?4?When calcined in air or vacuum,MOFs crystals are easy to be converted into porous MOFs based nanomaterials which with high specific surface area and more active sites.These materials not only have high water and chemical stability,but also can effectively increase the contact area between electrolyte and electrode,promote the transfer of electric charge at the electrolyte electrode interface,and increase the electrocatalytic activity.?5?The construction of self-supporting MOF-based nanomaterials is directly used for electrocatalysis,which can effectively avoid the defect of reducing the active sites caused by the use of adhesives,increase its active utilization rate,and increase its specific capacity.Therefore,this study is devoted to the controllable preparation and electrocatalytic application of high cost effective MOF based nanomaterials,including the following four parts:1.Study on anchoring CuO nanoparticles on C,N-codoped g-C₃N₄ nanosheets from melamine-entrapped MOF gel for high-efficiency oxygen evolution.The melamine-doped Cu-MOF gel was used as a precursor,and calcined and pyrolyzed at high temperature to prepare g-C₃N₄ nanosheet composites co-doped with CuO nanoparticles and C and N.The material exhibited excellent electro-catalytic performance of oxygen evolution?OER?and maintains the stability of long-term reactivity.2.Study on synchronously achieving highly efficient hydrogen evolution and high-yield synthesis of glucaric acid by Ni-MOF nanorod arrays.Ni-MOF precursors were deposited on the activated nickel foam by electrodeposition,and Ni-MOF nanorod array materials based on nickel foam were successfully prepared by low-temperature activation.The material exhibited good hydrogen evolution?HER?performance under alkaline conditions,and realized the selective oxidation of the anode sodium gluconate to glucaric acid at the same time.After optimization of multiple influence factors,the material has successfully achieved the high efficiency of HER and electro-oxidation of sodium gluconate to glucaric acid.3.Study on boosting electrocatalytic nitrogen fixation via energy-efficient anodic oxidation of sodium gluconate with Cu-MOF.By depositing Cu-MOF precursor on the nickel foam,a tightly arranged array of JUC-1000 nanorods was successfully prepared after activation.At the same time,this material has realized the bifunctional catalysis of the selective catalytic oxidation of glucose monoacid to glucose diacid and the reduction of electrochemical nitrogen to ammonia at the cathode,which further proves the significant improvement of the efficiency of nitrogen fixation by anodic oxidation and provides a new idea to improve the efficiency of nitrogen fixation.4.Study on the electrochemical recognition of penicillamine enantiomers by chiral macromolecule@MOF helix nanocomposites.In view of the high cost of chiral ligands,this study synthesized hydrophilic and lipophilic amphiphilic chiral macromolecules with a helical structure.Using this molecular material as a chiral template,a chiral macromolecule@MOF spiral nanocomposite was constructed.The material not only has high selective identification and quantitative analysis capabilities for the penicillamine enantiomer,but also has good stability.