CN110433861A - A kind of preparation method and application of self-supporting MOF nano-array composite catalyst - Google Patents

A kind of preparation method and application of self-supporting MOF nano-array composite catalyst Download PDF

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CN110433861A
CN110433861A CN201910813245.9A CN201910813245A CN110433861A CN 110433861 A CN110433861 A CN 110433861A CN 201910813245 A CN201910813245 A CN 201910813245A CN 110433861 A CN110433861 A CN 110433861A
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sala
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侯莹
匡轩
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University of Jinan
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22Organic complexes
    • B01J31/2204Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208Oxygen, e.g. acetylacetonates
    • B01J31/2226Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/2243At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00Catalysts, in general, characterised by their form or physical properties
    • B01J35/60Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/10Complexes comprising metals of Group I (IA or IB) as the central metal
    • B01J2531/16Copper
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84Metals of the iron group
    • B01J2531/845Cobalt

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Abstract

It is used for the application of electro-catalysis room temperature under nitrogen reduction the invention discloses a kind of preparation method of self-supporting MOF nano-array composite catalyst and based on the catalyst, belongs to catalysis technique, nanocomposite technical field.It, which has main steps that, mixes cupric perchlorate solution and ligand solution, and the precursor solution of electro-deposition Cu (II)-sala is made;In three-electrode system, using constant potential electrodeposition technology, the nano material of copper mesh loaded Cu (II)-sala is made;Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping, after washing, is placed in 250 W micro-wave ovens and activates, obtain self-supporting MOF nano-array composite catalyst;The catalyst is used for the application of electro-catalysis room temperature under nitrogen reduction, the catalyst preparation process to be simple, and energy consumption is small, and pollution is small, there is good industrial prospect.

Description

A kind of preparation method and application of self-supporting MOF nano-array composite catalyst
Technical field
The invention discloses a kind of preparation method of self-supporting MOF nano-array composite catalyst and it is based on the catalyst For the application of electro-catalysis room temperature under nitrogen reduction, belong to the fields such as catalysis technique, nanocomposite technology.
Background technique
Other than being used as the nitrogenous fertilizer of anhydrous solution or salt form, ammonia is as a kind of potential energy-accumulating medium and automobile-used substitution Fuel is receive a lot of attention.2015, ammonia preparation consumption energy accounted for the 2% of global energy.It has recently been demonstrated that logical Cross electrochemical method, N2And H2O can produce ammonia, compared with Haber-Bosch process, have zero CO2It discharges and energy-efficient excellent Gesture.However, since the theoretical inspiration of hydrogen conversion reaction (HER) and nitrogen reduction reaction (NRR) is very close, H2It is primary product, Because the former kinetics is very fast.The calculated results during showing NRR most of catalyst surfaces to reactant Absorption and proton/electronics transfer are all unfavorable.Other than low faradic efficiency, the formation speed of ammonia is another big problem slowly.Ammonia The highest response rate of electrochemistry formated is 1 × 10-8 mol NH3 s-2 cm-2, generated far below the common ammonia of commercial system fast Rate.So it is extremely urgent to synthesize high catalytic efficiency, highly selective catalyst.
MOFs is the material of extensive concern in recent years, because the specific surface area of MOFs material super large and porosity, special Cellular structure, opening metallic site, so that it is possessed huge adsorption capacity and delivered payload capability;Meanwhile MOFs material structure can It designs, is controllable, changing the advantages that very flexible.However the catalytic activity of MOFs and water stability are still up for improving.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, providing a kind of self-supporting MOF nanometers of battle arrays The preparation method of column composite catalyst, the preparation method simple process, energy consumption is small, there is good industrial prospect.
The two of technical assignment of the invention are to provide the purposes of the catalyst, i.e., the catalyst are used for electro-catalysis room temperature The application of nitrogen reduction.With very high catalytic efficiency and selectivity.
To achieve the above object, The technical solution adopted by the invention is as follows:
1. a kind of preparation method of self-supporting MOF nano-array composite catalyst
(1) electro-deposition precursor solution is prepared
By 0.8-1.0 mmol Cu (ClO4)2·6H2O and 1.6-2.0 mmol benzene is dissolved in 15-20 mL methanol MeOH solution, 180 W ultrasounds obtain clear cupric perchlorate solution to clarifying;
By 0.8-1.0 mmol ligand H2Sala and 0.8-1.0 mmol LiOH is added to 8-10 mL H2In O, 25-30 is stirred Min obtains clear ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.8-1.0 mmol Co (NO3)2·6H2O is dissolved in 8-10 mL H2In O, 180 W ultrasounds obtain clear to clarifying Cobalt nitrate solution;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum Helping electrode, calomel electrode is that reference electrode is deposited under the deposition voltage of -1.0 ~ -1.5 V using constant potential electrodeposition technology The nano material of copper mesh loaded Cu (II)-sala is made in 8-12 min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2-3 h, after washing, are placed in 250 W microwaves 3 min are activated in furnace, and copper mesh load C o is made2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nanometers of battle arrays Column composite catalyst.
The activation copper mesh, be by the copper mesh of the cm of 1.0 cm × 1.0 mass fraction be 1.5% dilute hydrochloric acid in 180 W ultrasound 2-4 min removes surface irregularities, is made after then being cleaned respectively with distilled water, ethyl alcohol.
Cu (the II)-sala, basic structural unit are [Cu2(sala)(phen)3](ClO4)2·2.5H2O is by 2 A Cu2+, 1 ligand sala2-, 3 benzene phen molecules, 2 ClO4 -Ion and 2.5 hydrones are constituted;The sala, structure It is as follows to make formula:
2. a kind of self-supporting MOF nano-array composite catalyst of preparation method preparation as described above is used for electro-catalysis The application of room temperature under nitrogen reduction, steps are as follows:
(1) standard curve is drawn
Ammonium chloride and concentration is used to prepare series NH for the KOH solution of 0.1 M4 +Standard solution;
2 mL standard solution are taken, the NaClO that 2 mL concentration are the NaOH solution of 1.0 M, 1 mL concentration is 0.05 M is sequentially added Solution, the sodium nitroprusside solution that 0.2 mL mass fraction is 1% quickly shake for several times, 25 DEG C of 2 h of placement, with UV- Vis spectrophotometer detects the absorbance peak at the 653 nm wavelength of solution, draws absorbance-concentration, that is, A-c standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction;
(2) electro-catalysis room temperature fixed nitrogen
Two Room electrochemical cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, The KOH solution that 30 mL are added in two Room, concentration is 0.1 M;Using three-electrode system, cathode chamber is placed in MOF nanometers of battle arrays of self-supporting Column composite catalyst is as working electrode, and Ag/AgCl is as reference electrode;Anode chamber is placed in platinized platinum as auxiliary electrode;Cathode Room is passed through N2After 30 min, N is restored using -0.8 ~ -1.2 V2Fixed nitrogen takes the reaction solution of 2 h of catalysis reaction, analyzes the dense of ammonia Degree, to test electro-catalysis room temperature fixed nitrogen performance;
The concentration of the analysis ammonia, method only react the reaction solution of 2 h, alternative steps with step (1) with 2 mL catalysis (1) 2 mL standard solution in calculate the yield of ammonia according to standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction.
When applied voltage is -0.1 V vs RHE, NH is reduced into for the catalyst room temperature under nitrogen3Rate be 25.3- 31.9 μg NH3 h−1 cm-2, faradic efficiency 12.3-14.6%.
The beneficial technical effect of the present invention is as follows:
(1) preparation of self-supporting MOF nano-array composite catalyst of the present invention is to use that easy-operating two-step method is facilitated to prepare, First is that the nano material of copper mesh loaded Cu (II)-sala is made in constant potential electrodeposition technology;Second is that by-sala nanometers of materials of Cu (II) Material is mixed with dipping with clear cobalt nitrate solution, and copper mesh load C o is made2+The nanocomposite of Cu (II)-sala is adulterated, it should Preparation method simple process, energy consumption is small, there is good industrial prospect.
(2) it is activated in 250 W micro-wave ovens of the invention, activation efficiency is high, self-supporting MOF nano-array composite catalyzing obtained Agent is stablized, and after being recycled 10 times, the change of catalytic activity and faradic efficiency can be ignored;The catalyst is used for electricity It is catalyzed the application of room temperature under nitrogen reduction, microwave activation exposes more active sites, greatly improves the specific surface of catalyst Product, Co obtained2+The nano material synergistic effect for adulterating Cu (II)-sala is significant, and catalysis fixed nitrogen ammonification activity increases, selectivity Also more preferable.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.
A kind of preparation method of the self-supporting MOF nano-array composite catalyst of embodiment 1
(1) electro-deposition precursor solution is prepared
By 0.8 mmol Cu (ClO4)2·6H2O and 1.6 mmol benzene are dissolved in 15 mL methanol MeOH solution, and 180 W ultrasounds are to clear Clearly, clear cupric perchlorate solution is obtained;
By 0.8 mmol ligand H2Sala and 0.8 mmol LiOH are added to 8 mL H2In O, 25 min are stirred, are clarified Ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.8 mmol Co (NO3)2·6H2O is dissolved in 8 mL H2In O, it is molten to obtain clear cobalt nitrate to clarifying for 180 W ultrasounds Liquid;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum Electrode, calomel electrode is helped to deposit 8 min under the deposition voltage of -1.0 V using constant potential electrodeposition technology for reference electrode, The nano material of copper mesh loaded Cu (II)-sala is made;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2 h, after washing, are placed in 250 W micro-wave ovens Copper mesh load C o is made in 3 min of middle activation2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nano-array Composite catalyst;
Cu (the II)-sala, basic structural unit are [Cu2(sala)(phen)3](ClO4)2·2.5H2O is by 2 Cu2+, 1 ligand sala2-, 3 benzene phen molecules, 2 ClO4 -Ion and 2.5 hydrones are constituted;The sala, construction Formula is as follows:
A kind of preparation method of the self-supporting MOF nano-array composite catalyst of embodiment 2
(1) electro-deposition precursor solution is prepared
By 0.9 mmol Cu (ClO4)2·6H2O and 1.8 mmol benzene are dissolved in 17 mL methanol MeOH solution, and 180 W ultrasounds are to clear Clearly, clear cupric perchlorate solution is obtained;
By 0.9 mmol ligand H2Sala and 0.9 mmol LiOH are added to 9 mL H2In O, 27 min are stirred, are clarified Ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.9 mmol Co (NO3)2·6H2O is dissolved in 9 mL H2In O, it is molten to obtain clear cobalt nitrate to clarifying for 180 W ultrasounds Liquid;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum Electrode, calomel electrode is helped to deposit 10 under the deposition voltage of -1.2 V using constant potential electrodeposition technology for reference electrode The nano material of copper mesh loaded Cu (II)-sala is made in min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2.5 h, after washing, are placed in 250 W microwaves 3 min are activated in furnace, and copper mesh load C o is made2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nanometers of battle arrays Column composite catalyst;
The structure of Cu (the II)-sala is the same as embodiment 1.
A kind of preparation method of the self-supporting MOF nano-array composite catalyst of embodiment 3
(1) electro-deposition precursor solution is prepared
By 1.0 mmol Cu (ClO4)2·6H2O and 2.0 mmol benzene are dissolved in 20 mL methanol MeOH solution, and 180 W ultrasounds are to clear Clearly, clear cupric perchlorate solution is obtained;
By 1.0 mmol ligand H2Sala and 1.0 mmol LiOH are added to 10 mL H2In O, 30 min are stirred, are clarified Ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 1.0 mmol Co (NO3)2·6H2O is dissolved in 10 mL H2In O, 180 W ultrasounds obtain clear cobalt nitrate to clarifying Solution;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum Electrode, calomel electrode is helped to deposit 12 under the deposition voltage of -1.5 V using constant potential electrodeposition technology for reference electrode The nano material of copper mesh loaded Cu (II)-sala is made in min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 3 h, after washing, are placed in 250 W micro-wave ovens Copper mesh load C o is made in 3 min of middle activation2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nano-array Composite catalyst;
The structure of Cu (the II)-sala is the same as embodiment 1.
Embodiment 4
Copper mesh is activated described in embodiment 1-3, is the dilute hydrochloric acid for being 1.5% in mass fraction by the copper mesh of the cm of 1.0 cm × 1.0 In 180 W ultrasound 2-4 min remove surface irregularities, it is obtained after then being cleaned respectively with distilled water, ethyl alcohol.
Embodiment 5
Embodiment 1 or embodiment 2 or self-supporting MOF nano-array composite catalyst described in embodiment 3 are used for electro-catalysis room temperature The application of nitrogen reduction
(1) standard curve is drawn
Ammonium chloride and concentration is used to prepare series NH for the KOH solution of 0.1 M4 +Standard solution;
Take 2 mL standard solution, sequentially add 2 mL concentration are the NaOH solution of 1.0 M, 1 mL concentration is 0.05 M NaClO, The sodium nitroprusside solution that 0.2 mL mass fraction is 1% quickly shakes for several times, and 25 DEG C of 2 h of placement are divided with UV-vis Photometer detects the absorbance peak at the 653 nm wavelength of solution, draws absorbance-concentration, that is, A-c standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction;
(2) electro-catalysis room temperature fixed nitrogen
Two Room electrochemical cell of H-type is connected on electrochemical workstation, is separated between two Room with 115 proton exchange membrane of Nafion, The KOH solution that 30 mL are added in two Room, concentration is 0.1 M, using three-electrode system, cathode chamber is placed in MOF nanometers of battle arrays of self-supporting Column composite catalyst is as working electrode, and Ag/AgCl is as reference electrode;Anode chamber is placed in platinized platinum as auxiliary electrode;Cathode Room is passed through N2After 30 min, N is restored using -0.8 ~ -1.2 V2Fixed nitrogen takes the reaction solution of 2 h of catalysis reaction, analyzes the dense of ammonia Degree, to test electro-catalysis room temperature fixed nitrogen performance;
The concentration of the analysis ammonia, method only react the reaction solution of 2 h, alternative steps with step (1) with 2 mL catalysis (1) 2 mL standard solution in calculate the yield of ammonia according to standard curve;
The NaOH solution of 1.0 M is 5% salicylic acid and sodium citrate containing mass fraction.
(4) when applied voltage is -0.1 V vs RHE, catalyst room temperature under nitrogen prepared by embodiment 1 is reduced into NH3 Rate be 25.3 μ gNH3 h−1 cm-2, faradic efficiency 12.3%;Catalyst room temperature under nitrogen prepared by embodiment 2 is reduced into NH3Rate be 31.9 μ gNH3 h−1 cm-2, faradic efficiency 14.6%;Catalyst prepared by embodiment 3, room temperature under nitrogen is also Original is at NH3Rate be 27 μ gNH3 h−1 cm-2, faradic efficiency 13%.

Claims (4)

1. a kind of preparation method of self-supporting MOF nano-array composite catalyst, which is characterized in that steps are as follows:
(1) electro-deposition precursor solution is prepared
By 0.8-1.0 mmol Cu (ClO4)2·6H2O and 1.6-2.0 mmol benzene is dissolved in 15-20 mL methanol MeOH solution, 180 W ultrasound obtains clear cupric perchlorate solution to clarifying;
By 0.8-1.0 mmol ligand H2Sala and 0.8-1.0 mmol LiOH is added to 8-10 mL H2In O, 25-30 is stirred Min obtains clear ligand solution;
Cupric perchlorate solution and ligand solution are mixed, the precursor solution of electro-deposition Cu (II)-sala is obtained;
By 0.8-1.0 mmol Co (NO3)2·6H2O is dissolved in 8-10 mL H2In O, 180 W ultrasounds obtain clear nitre to clarifying Acidic cobalt solution;
(2) electro-deposition prepares self-supporting MOF nano-array composite catalyst
Using electrochemical workstation three-electrode system, the activation copper mesh of the cm of 1.0 cm × 1.0 is working electrode, supplemented by platinized platinum Helping electrode, calomel electrode is that reference electrode is deposited under the deposition voltage of -1.0 ~ -1.5 V using constant potential electrodeposition technology The nano material of copper mesh loaded Cu (II)-sala is made in 8-12 min;
Cu (II)-sala nano material and clear cobalt nitrate solution are mixed with dipping 2-3 h, after washing, are placed in 250 W microwaves 3 min are activated in furnace, and copper mesh load C o is made2+Adulterate the nanocomposite of Cu (II)-sala, i.e. self-supporting MOF nanometers of battle arrays Column composite catalyst.
2. a kind of preparation method of self-supporting MOF nano-array composite catalyst according to claim 1, feature exist In the activation copper mesh is that 180 W are ultrasonic in the dilute hydrochloric acid that mass fraction is 1.5% by the copper mesh of the cm of 1.0 cm × 1.0 2-4 min removes surface irregularities, is made after then being cleaned respectively with distilled water, ethyl alcohol.
3. a kind of preparation method of self-supporting MOF nano-array composite catalyst according to claim 1, feature exist In Cu (the II)-sala, basic structural unit is [Cu2(sala)(phen)3](ClO4)2·2.5H2O is by 2 Cu2 +, 1 ligand sala2-, 3 benzene phen molecules, 2 ClO4 -Ion and 2.5 hydrones are constituted;The sala, structural formula is such as Under:
4. a kind of self-supporting MOF nano-array composite catalyst of preparation method preparation according to claim 1 is for electricity It is catalyzed the application of room temperature under nitrogen reduction.
CN201910813245.9A 2019-08-30 2019-08-30 Preparation method and application of self-supporting MOF (Metal organic framework) nano-array composite catalyst Expired - Fee Related CN110433861B (en)

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