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CN-115572391-A - Cadmium metal organic framework material and preparation method and application thereof

CN115572391ACN 115572391 ACN115572391 ACN 115572391ACN-115572391-A

Abstract

The invention discloses a cadmium metal organic framework material, a preparation method and application thereof, wherein a TENG device with excellent cycle stability is constructed by using a cadmium metal organic framework material Cd-MOF, and the TENG device is applied to self-driven cathode metal corrosion prevention. The Cd-MOF can be controllably synthesized by a solvothermal method, the selection range of a friction electrode material is expanded, the electric output performance of a friction nano-generator is improved, a TENG device constructed by the Cd-MOF material is applied to metal corrosion protection with a self-power supply characteristic, a novel friction material with good output performance and excellent circulation stability are constructed, the TENG device is prepared and applied to cathode protection of a Q235 steel sheet, and the metal corrosion protection function driven by self-power supply is realized.

Inventors

  • HUANG CHAO
  • ZHANG QIANG
  • MI LIWEI
  • ZHANG YINGYING
  • CHANG HONG
  • ZHANG YUE
  • Liu Saiwei
  • WANG FEI
  • WANG DANDAN

Assignees

  • UNIV ZHONGYUAN TECHNOLOGY

Dates

Publication Date
20230106
Application Date
20221019
Priority Date
20221019

Claims (10)

  1. 1. A preparation method of a cadmium metal organic framework material is characterized by comprising the following steps: (1) Adding Cd (NO) 3 ) 2 ·4H 2 O, ligand H 4 Adding CBBD and bridging ligand 4,4 \697-bpe into a mixed solvent consisting of water and acetonitrile, and uniformly stirring and mixing to obtain a mixed solution; (2) And (2) putting the mixed liquid obtained in the step (1) into a polytetrafluoroethylene lining reaction kettle, putting the filled reaction kettle into an oven for hydrothermal reaction, cooling and closing the oven after the reaction is finished, waiting for natural cooling to room temperature, then filtering, standing, and naturally drying to obtain colorless Cd-MOF particles, namely the cadmium metal organic framework material.
  2. 2. The method of claim 1, wherein the method comprises: cd (NO) in the step (1) 3 ) 2 ·4H 2 O, ligand H 4 The molar ratio of CBBD to bridging ligand 4,4 \ 697.
  3. 3. The method of claim 1, wherein the metal organic framework material comprises: in the step (1), 0.1mmolCd (NO) is used 3 ) 2 ·4H 2 Based on O, 3-5ml of water and 3-5ml of acetonitrile are needed.
  4. 4. The method of claim 1, wherein the metal organic framework material comprises: the temperature of the hydrothermal reaction in the step (2) is 160-170 ℃, and the time of the hydrothermal reaction is 60-72h.
  5. 5. The method of claim 1, wherein the metal organic framework material comprises: and (3) stopping cooling and closing the oven after the temperature in the step (2) is reduced to 80 ℃ at the speed of 5 ℃/h.
  6. 6. The cadmium metal organic framework material prepared by the preparation method of any one of claims 1 to 5, wherein the molecular structure of the cadmium metal organic framework material Cd-MOF is [ Cd (BBPD) (4,4 \697-bpe) H 2 O] n N = ∞ belonging to monoclinic system, space group is P2 1 N, unit cell parameters a =11.598 (3) a α =90, b =13.001 (7) a β =95.294 (10), c =40.453 (12) a γ =90.
  7. 7. A triboelectric nanogenerator TENG constructed using the cadmium metal organic framework material as defined in claim 6 as a triboelectric electrode material.
  8. 8. Use of a triboelectric nanogenerator TENG according to claim 7 in the corrosion protection of metals, characterized in that: the method for protecting metal by utilizing the output characteristic of the cadmium metal organic framework material Cd-MOF on the friction nanogenerator to realize metal corrosion prevention comprises the following steps: a. weighing a proper amount of Cd-MOF crystal material, and fully grinding the Cd-MOF crystal material to crystal powder with the size of 1-20 mu m by using a mortar; b. cutting into 5 × 6cm 2 The four corners of the copper sheet are stuck by transparent adhesive tapes and fixed on a cleaned operation table; c. transferring the crystal powder in the step a to the copper sheet in the step b, and uniformly coating to obtain the copper sheet coated with Cd-MOF powder; d. step cFixing copper wires on the back of the copper sheet by epoxy resin silver adhesive, sticking the copper sheet by using transparent adhesive tape, and cutting the copper sheet into 5 multiplied by 5cm 2 Obtaining the friction nano generator anode; e. repeating the steps b and d, using 5X 6cm 2 The copper sheet is adhered to a Kapton film containing a polyvinylidene fluoride PVDF film to prepare a friction nano generator cathode; f. assembling the device phases prepared in the steps d and e into a powder Cd-MOF-TENG device; g. and d, assembling the positive and negative plates prepared in the steps d and e on a friction nano generator, and outputting the output positive and negative plates to an anti-corrosion device through a wire, wherein the output positive electrode is connected with a platinum plate electrode, and the output negative electrode is connected with a polytetrafluoroethylene platinum plate electrode clamp clamped with a Q235 metal steel sheet.
  9. 9. Use according to claim 8, characterized in that: one end of the anti-corrosion device is a platinum sheet electrode, the other end of the anti-corrosion device is a polytetrafluoroethylene platinum sheet electrode clamp for clamping a Q235 steel sheet, and a device solution is a NaCl aqueous solution with the mass fraction of 3.5%, so that the seawater environment is simulated.
  10. 10. Use according to claim 9, characterized in that: under the condition of not applying external circuit protection, the metal is subjected to microscopic observation in the environments of NaCl aqueous solution with the mass fraction of 3.5% within 0h, 3h, 6h and 9h respectively, so that the metal is obviously and rapidly corroded; when the TENG friction nanogenerator filled with Cd-MOF is applied, observation is carried out at the same time to find that the corrosion trend is effectively restrained, metal is well protected, and no obvious corrosion phenomenon occurs.

Description

Cadmium metal organic framework material and preparation method and application thereof Technical Field The invention belongs to the technical field of organic energy storage, and particularly relates to synthesis of a nano-structure metal organic framework material Cd-MOF and application of a friction nano-generator (TENG) constructed by using the nano-structure metal organic framework material Cd-MOF as an electrode material to metal corrosion prevention. Background With the energy exhaustion caused by the exploitation and use of some non-renewable resources on the earth and the environmental problems caused by the energy exhaustion, the problem is an urgent problem that people have to face, and the use of clean energy becomes an indispensable choice for sustainable development. Friction nano-generators are widely studied and applied in different fields due to their characteristics of low cost, easy manufacturing, high output power and high conversion efficiency. In the process, methods for improving the output performance of the friction nano-generator by changing the friction materials of the positive electrode and the negative electrode, increasing the dielectric constant and the like are widely researched, however, the realization of a continuous energy conversion process by using systems and complex molecular designs of the materials still has a considerable challenge. Metal Organic Framework (MOF) materials are a class of coordination compounds formed by coordination bonds between a metal/metal cluster and an organic bridging ligand. Due to the large specific surface area and the unique three-dimensional holes, a series of stable MOFs with excellent applicable values are gradually developed and widely applied to the advanced fields of gas adsorption and separation, catalysis, medicines and the like. Meanwhile, the MOF is a unique framework structure formed by metal or metal clusters and organic bridging ligands, so that effective transmission among electrons is facilitated, and a new theoretical basis and application value are provided for the MOF material serving as a friction electrode material to regulate and control the output performance of the friction nano-generator. In addition, china is the largest iron and steel producing country in the world, however, the loss caused by iron and steel rusting due to metal oxidation every year is immeasurable, so that the invention of the corrosion prevention equipment with low cost and good protection effect has important significance. Friction nano-generators have been widely studied and applied in various fields due to their low manufacturing cost, high output power and high conversion efficiency. The MOF and the friction nano-generator are combined to generate electricity, and a cathodic protection method is used for protecting metal, so that an effective way is provided, and meanwhile, the cost and the protection requirements are met. Disclosure of Invention Aiming at the problems in the prior art, the invention discloses a TENG device constructed by taking a Cd-MOF material with a three-dimensional structure as a friction electrode material, which has good output performance and excellent cycle stability and is applied to self-driving to realize metal corrosion prevention of Q235 steel. Therefore, the material can become a potential high-output friction electrode material. The invention utilizes H 4 CBBD （4',4'''-carbonylbis(([1,1'-biphenyl]3,5-dicarboxylic acid) is used as a multifunctional organic ligand, cd-MOF material with a three-dimensional structure is constructed by self-assembly with cadmium ions and bridging ligand 1,2-Di (4-pyridine) ethylene (4, 4 \697-bpe), and is used as a friction electrode material to form a TENG device, and a cathodic protection corrosion prevention strategy is executed to realize metal corrosion prevention of self-driven Q235 steel. In order to solve the technical problem, the invention adopts the following technical scheme: the invention relates to a preparation method of a three-dimensional structure Cd-MOF material, which comprises the following steps: (1) Cadmium nitrate (Cd (NO) 3 ) 2 ·4H 2 O), ligand H 4 CBBD (H 4 CBBD = 4',4'''-carbonylbis(([1,1'-biphenyl]-3,5-dicarboxylic acid))), 4 \ 697-bpe, (1, 2-bis (4-pyridyl)), water (3-5 ml) and acetonitrile (3-5 ml) were mixed well; (2) Putting the mixed solution obtained in the step (1) into a 25 mL polytetrafluoroethylene lining reaction kettle; (3) Putting the reaction kettle filled in the step (2) into an oven, setting the temperature to be 160-170 ℃, keeping the temperature for 60-72h, then cooling to 80 ℃ at the speed of 5 ℃/h, stopping cooling, closing the oven, and waiting for natural cooling to room temperature; (4) And (4) transferring the Cd-MOF cooled in the step (3) from the inner liner of the reaction kettle to filter paper by using a dropper, standing, and naturally drying to obtain colorless Cd-MOF particles, namely the cadmium metal organic framewor