CN106784895A - A kind of CO selective methanations Ni/ZrO based on Zr MOF structures2Catalyst and preparation method thereof - Google Patents

A kind of CO selective methanations Ni/ZrO based on Zr MOF structures2Catalyst and preparation method thereof Download PDF

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CN106784895A
CN106784895A CN201710008930.5A CN201710008930A CN106784895A CN 106784895 A CN106784895 A CN 106784895A CN 201710008930 A CN201710008930 A CN 201710008930A CN 106784895 A CN106784895 A CN 106784895A
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mof
catalyst
zro
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董新法
平丹
耿建铭
封啸
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9041—Metals or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8878—Treatment steps after deposition of the catalytic active composition or after shaping of the electrode being free-standing body
    • H01M4/8882—Heat treatment, e.g. drying, baking
    • H01M4/8885—Sintering or firing
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a kind of CO selective methanations Ni/ZrO based on Zr MOF structures2Catalyst and preparation method thereof.The Ni/ZrO2Catalyst main active is Ni, and carrier is ZrO2；The specific surface area of catalyst is 55 ~ 98 m2/ g, aperture is 9.0 ~ 16.2 nm, and the load capacity of Ni is 5 ~ 15 wt%.The inventive method includes step：（1）The preparation of metal-organic framework materials Zr MOF；（2）Ni/ZrO2The preparation of catalyst.Ni/ZrO of the invention2Catalyst has excellent CO methanation activities, can be interval in reaction temperature wide（210~350℃）With reacting gas air speed（4000~20000 h‑1）Content is down to 10 below ppm for the CO of 1vol% in the lower gas by reformation, and selectivity is higher than 50%.

Description

A kind of CO selective methanations Ni/ZrO based on Zr-MOF structures2Catalyst and its system Preparation Method
Technical field
The present invention relates to catalyst preparation technical field, it is specifically related to for CO selective methanations in hydrogen-rich gas Catalyst and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells（PEMFC）, because with efficiency high, the small, operating temperature of pollution is low, startup is fast, power The advantages of density is high, it has also become the substitution most competitive dynamic origin of gasoline engine automobile.PEMFC is with hydrogen-rich reformed gas It is that Pt electrode pairs CO is extremely sensitive in fuel, but PEMFC, a small amount of CO can make it be poisoned and reduce battery performance, therefore must CO a small amount of in hydrogen-rich gas must be removed, its concentration is down to the tolerance level of fuel cell Pt electrodes（10 below ppm）. CO selective methanations need not add additional reactant, can directly utilize raw material H2The first harmless to PEMFC with CO reaction generations Alkane, it is considered to be remove the effective ways of a small amount of CO online.But due to often containing a large amount of CO in hydrogen-rich gas2, CO2Competition Methanation certainly will cause a large amount of H2Loss；Additionally, also easily there is reverse water-gas-shift reaction generation CO at high temperature.Therefore, In order to meet requirements of the PEMFC for hydrogen quality, it is necessary to which exploitation one kind has high activity, high selection in operation temperature wider The CO selective methanation catalysts of property and high stability.
Methanation reaction catalyst is generally solid supported, mainly has noble metal Ru bases and non-noble metal Ni-based urges Agent, wherein Ni bases catalyst are cheap and easy to get, and under appropriate preparation process condition, its methanation activity is catalyzed with Ru bases substantially Agent is quite even better, is considered as always good methanation catalyst.For Ni base catalyst, common carrier has Al2O3、TiO2、ZrO2、SiO2, MgO etc..Takenaka etc. [International journal of hydrogen energy, 29(2004):1065-1073] research show：The CO methanation reactions activity order of Ni bases catalyst is on different carriers：Ni/ MgO<Ni/Al2O3<Ni/SiO2<Ni/TiO2<Ni/ZrO2.Although Ni catalyst has obtained industrial applications, actually should The problems such as difficult reduction of active component, low catalysis activity and poor stability are still suffered from during.The decentralization of active component is always It is a key factor for influenceing catalyst catalytic performance, and carrier structure and specific surface area are influence active component decentralization One of principal element, the carrier for choosing bigger serface is conducive to improving catalytic performance.
MOF（Metal-organic framework）Material as a kind of new functional material, with larger specific surface area and rule Pore passage structure, its not only for active component preferably disperses to provide good condition, and can inhibitory activity component sintering Aggregation.Additionally, containing substantial amounts of metal ion in MOF structures, porous metals oxidation can be prepared as template or predecessor Thing nano material.Because MOF skeleton structures are at least partially retained in the structure of respective metal oxide in heating process, because Oxide obtained by this has specific surface area higher than oxide prepared by prior art.Singh etc. is with MOF materials ZIF-8 Ni, Ni-Pt metallic catalyst of a series of high dispersives are prepared for for carrier, and have investigated its product hydrogen in hydrazine hydrate solution Can [Chemcatchem, 5 (2013):3000-3004].Liu etc. is calcined back loading Ru systems with ZIF-67 as precursor and template Standby Ru/Co3O4- MOF catalyst shows toluene oxidation performance high [RSC advances, 5 (2015): 52066- 52071].Chen etc. is with Cu3(BTC)2The CuO/CeO obtained in presoma2Catalyst, it is found that activated centre species have very high Dispersiveness, and this catalyst has good activity [Catalysis communication, 26 for CO preferential oxidations (2012): 25-29]。
Patent application CN201310119360.9 discloses a kind of based on Cu3(BTC)2·nH2O prepares CuO multi-stage nano knots The method of structure.Patent application CN201510805068.1 discloses one kind and does predecessor using metal organic framework MOF-5 materials, Size uniformity is prepared by the method for self assembly, crystallinity is higher, the larger porous zinc bloom microballoon of specific surface area.Patent Shen Please CN201210422400.2, CN201210422382.8, CN201210535655.X and CN201510089157.0 announce It is the method that carrier prepares dispersed catalysts with MOF materials.
At present, from the point of view of existing report, it is showed no with macropore structure and bigger serface and high heat stability Property MOF materials prepare supported Ni catalyst and for CO selective methanations in hydrogen-rich gas as precursor and template Report.
The content of the invention
The defect not high enough it is an object of the invention to be directed to existing Ni bases catalyst activity, selectivity, stability, there is provided A kind of CO selective methanations Ni/ZrO based on Zr-MOF structures2Catalyst.The Ni/ZrO2Catalyst not only high efficiency low cost, and And with reaction temperature interval wide, high selectivity and stability, can be in reaction temperature interval wide by hydrogen-rich gas CO deep removals, meet requirement of the FC-EV to high-quality hydrogen source well.
A kind of CO selective methanations Ni/ZrO based on Zr-MOF structures of the present invention2The main active component of catalyst is Ni, carrier is ZrO2；The specific surface area of catalyst is 55 ~ 98 m2/ g, aperture is 9.0 ~ 16.2 nm, the load capacity of Ni for 5 ~ 15wt%。
A kind of CO selective methanations Ni/ZrO based on Zr-MOF structures of the present invention2Catalyst is applied to contained CO concentration Scope 0.5 ~ 2vol% hydrogen-rich gas, with preferable less than 1vol%.
Another object of the present invention is to provide a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures2 The preparation method of catalyst.The method with metal organic framework Zr-MOF as precursor and template, using infusion process carried metal After Ni, further roasting reduction obtains the CO selective methanations Ni/ZrO based on Zr-MOF structures2Catalyst.
A kind of CO selective methanations Ni/ZrO based on Zr-MOF structures2The preparation method of catalyst, including following step Suddenly：
（1）The preparation of metal-organic framework materials Zr-MOF：By ZrCl4, terephthalic acid (TPA)（BDC, part）With dimethyl formyl Amine（DMF, solvent）Uniform mixing, thermostatic crystallization；After crystal is dried through dimethylformamide, methyl alcohol washing, again with methanol immersion, Centrifugation, white powder, i.e., described metal-organic framework materials Zr-MOF are obtained after drying；
（2）Ni/ZrO2The preparation of catalyst：Obtained metal-organic framework materials Zr-MOF is added to NiCl2·6H2O is molten Impregnated in liquid, and stirred at room temperature, be centrifuged, dried, roasting, reduction obtains the Ni/ZrO2Catalyst.
Further, step（1）In, the ZrCl4, terephthalic acid (TPA) and dimethylformamide mol ratio be 1:1: 150 ~ 500, preferably 1:1:180.
Further, step（1）In, the temperature of the crystallization is 110 ~ 130 DEG C, preferably 120 DEG C.
Further, step（1）In, the h of time 24 ~ 72 of the crystallization, preferably 24 h.
Further, step（1）In, the time of the methyl alcohol immersion is 3 ~ 5 days, and the methyl alcohol for more renewing daily.
Further, step（1）In, the dry temperature is 65 ~ 75 DEG C.
Further, step（2）In, metal-organic framework materials Zr-MOF and NiCl2·6H2O is in unit volume solution In quality proportioning be 1:0.024 ~ 2.4, preferably 1:0.12~1.44.
Further, step（2）In, NiCl2·6H2The solvent of O solution is water or ethanol.
Further, step（2）In, metal-organic framework materials Zr-MOF is in NiCl2·6H2In O solution stir when Between be 5 ~ 24 h, preferably 12 h.
Further, step（2）In, the dry temperature is 65 ~ 75 DEG C.
Further, step（2）In, the roasting is to be calcined in air atmosphere, and the temperature of roasting is 400 ~ 550 DEG C, Preferably 450 DEG C.
Further, step（2）In, the time of the roasting is 2 ~ 4h, preferably 3 h.
Further, step（2）In, the atmosphere of the reduction is 20 vol%H2-N2Gaseous mixture atmosphere.
Further, step（2）In, the temperature of the reduction is 350 ~ 450 DEG C, preferably 350 DEG C.
Further, step（2）In, the time of the reduction is 1 ~ 2h, preferably 1.5h.
Compared with prior art, the invention has the advantages that and beneficial effect：
（1）CO selective methanation Ni/ZrO of the present invention based on Zr-MOF structures2There is catalyst excellent CO methanations to live Property, can be interval in reaction temperature wide（210~350℃）With reacting gas air speed（4000~20000 h-1）In the lower gas by reformation Content is down to 10 below ppm for the CO of 1vol%, and selectivity is higher than 50%, disclosure satisfy that FC-EV to Gao Pin The demand of matter hydrogen source；
（2）CO selective methanation Ni/ZrO of the present invention based on Zr-MOF structures2Catalyst has good catalytic stability, Sustained response 120 h, CO exit concentration is in 10 below ppm at 240 DEG C of reaction temperature, and keeps 100% selectivity, gram The defect containing Ni poor catalyst stabilities is taken；
（3）CO selective methanation Ni/ZrO of the present invention based on Zr-MOF structures2Catalyst is with MOF structures as template and preceding body Body, prepares Ni/ZrO2The specific surface area of catalyst is higher, and active component Ni dispersivenesses are more preferably, cheap；
（4）Preparation method of the present invention is simple to operate, can be applied to the hydrogen-feeding system of PEMFC.
Brief description of the drawings
Fig. 1 is the XRD of the metal-organic framework materials Zr-MOF of preparation in embodiment 1；
Fig. 2 is that the metal-organic framework materials Zr-MOF single crystal datas of preparation in embodiment 1 simulate the XRD for obtaining；
Fig. 3 is the SEM figures of the metal-organic framework materials Zr-MOF of preparation in embodiment 1；
Fig. 4 is the TEM figures of the metal-organic framework materials Zr-MOF of preparation in embodiment 1；
Fig. 5 is the Ni/ZrO of preparation in embodiment 12The TEM figures of catalyst；
Fig. 6 a and Fig. 6 b are the Ni/ZrO of preparation in embodiment 12The CO methanation reactions activity figure of catalyst；
Fig. 7 is the Ni/ZrO of preparation in embodiment 12The stability test design sketch of the CO methanation performances of catalyst；
Fig. 8 a and Fig. 8 b are the Ni/ZrO of preparation in embodiment 52The CO methanation reactions activity figure of catalyst.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this, Also include any combination between each specific embodiment.
Embodiment catalyst performance is tested：Catalyst 0.1g prepared by Example, loads the quartz that internal diameter is 6 mm anti- Ying Guanzhong, is then 9000 h with air speed-1It is passed through 79vol% H2、20vol% CO2, 1vol% CO gaseous mixture, reaction temperature 140 ~ 400 DEG C of intervals of degree, test catalyst carries out selective methanation activity and selectivity to the CO of low content in hydrogen-rich gas, Product is monitored on-line by gas-chromatography.
Embodiment 1
（1）The preparation of metal-organic framework materials Zr-MOF：By ZrCl4, BDC and DMF is with mol ratio 1:1:180 uniform mixing Afterwards, 120 DEG C of h of crystallization 24, centrifugation is washed three times with DMF and methyl alcohol successively, and 65 DEG C of drying obtain white powder；To obtain White powder soaked three days with methanol solvate, and change methyl alcohol daily, the part that will remain in sample and solvent molecule displacement Out, the white powder of last gained obtains metal-organic framework materials Zr-MOF in 65 DEG C of dryings；
The XRD that XRD and its single crystal data simulation of the metal-organic framework materials Zr-MOF of preparation are obtained is respectively such as Fig. 1 With shown in Fig. 2, it can be seen that the XRD diffraction that main diffraction peak and the single crystal data simulation of the Zr-MOF of synthesis are obtained Peak coincide substantially, illustrates successfully to synthesize Zr-MOF；
The SEM of the metal-organic framework materials Zr-MOF of preparation is schemed as shown in figure 3, it can be seen that metal-organic bone Frame material Zr-MOF grain size distributions are uniform, and particle diameter is smaller；
The TEM of the metal-organic framework materials Zr-MOF of preparation is schemed as shown in figure 4, it can be seen that metal-organic bone Frame material Zr-MOF grain size distributions are uniform, and size is about 13nm；
（2）8 ml concentration are taken for 0.024 g/ml NiCl2·6H2The ethanol solution of O, be stirring evenly and then adding into 0.2 g metals- Organic framework material Zr-MOF, the at room temperature h of high degree of agitation 12, after centrifugation, 65 DEG C of dryings in Muffle furnace 450 DEG C of 3 h of roasting, 20vol% H2-N2After 1.5 h of the lower 350 DEG C of reduction of mixed-gas atmosphere, methanation Ni/ZrO is obtained final product2Catalyst.The Ni/ of preparation ZrO2The specific surface area of catalyst is 98 m2/ g, aperture is 9.4 nm, and the load capacity of Ni is 13 wt%.
Ni/ZrO manufactured in the present embodiment2The TEM of catalyst is schemed as shown in figure 5, it can be seen that Ni/ZrO2Catalysis Agent grain size distribution is uniform.
Ni/ZrO manufactured in the present embodiment2The CO exit concentrations and CH of catalyst4Exit concentration is varied with temperature respectively as schemed Shown in 6a and Fig. 6 b, it can be seen that Ni/ZrO2The catalyst middle CO that can make to work off one's feeling vent one's spleen in the range of 215-345 DEG C, is dense Degree is down to 10 below ppm, while keeping CH4Concentration is less than 2%, i.e., selectivity is more than 50%.
Ni/ZrO manufactured in the present embodiment2The CO methanation stability test effects of catalyst are as shown in fig. 7, can from figure To find out, the h of follow-on test 120 at being 240 DEG C in reaction temperature, its CO exit concentration is in 10 below ppm（About 1 ppm）, And keep CH4Concentration is less than 1%, i.e., selective close to 100%.
Embodiment 2
（1）By ZrCl4, BDC and DMF is with mol ratio 1:1:After 150 uniform mixing, 110 DEG C of h of crystallization 36, centrifugation, successively Washed with DMF and methyl alcohol three times, 70 DEG C of drying obtain white powder；The white powder that will be obtained is soaked three days with methanol solvate, And methyl alcohol is changed daily, the part and solvent molecule that will be remained in sample are cemented out, and the white powder of last gained is in 70 DEG C Dry, obtain metal-organic framework materials Zr-MOF；
（2）It is 6 × 10 to take 8 ml concentration-4 g/ml NiCl2·6H2The aqueous solution of O, is stirring evenly and then adding into 0.2 g pretreatments Zr-MOF afterwards, at room temperature high degree of agitation 12h, after centrifugation, 70 DEG C of dryings in Muffle furnace 550 DEG C of roastings 2 h, 20% H2-N2It is mixed After closing the lower 450 DEG C of reductase 12 h of gas atmosphere, that is, obtain methanation Ni/ZrO2Catalyst.
The Ni/ZrO of preparation2The specific surface area of catalyst is 55 m2/ g, aperture is 16.2 nm, and the load capacity of Ni is 5 wt%。
CO methanations test result indicate that：Catalyst keeps activity higher in reaction temperature, wherein in reaction temperature The middle CO concentration that can make to work off one's feeling vent one's spleen between 220 ~ 320 DEG C of degree is down to below 10ppm, and keeps selectivity to be not less than 50%.
Embodiment 3
（1）By ZrCl4, BDC and DMF is with mol ratio 1:1:After 250 uniform mixing, 130 DEG C of h of crystallization 72, centrifugation, successively Washed with DMF and methyl alcohol three times, 65 DEG C of drying obtain white powder；The white powder that will be obtained is soaked three days with methanol solvate, And methyl alcohol is changed daily, the part and solvent molecule that will be remained in sample are cemented out, and the white powder of last gained is in 75 DEG C Dry, obtain metal-organic framework materials Zr-MOF；
（2）It is 6 × 10 to take 8 ml concentration-3 g/ml NiCl2·6H2The ethanol solution of O, is stirring evenly and then adding into 0.2 g and locates in advance Zr-MOF after reason, the h of high degree of agitation 5, centrifugation, after 75 DEG C of dryings in Muffle furnace 450 DEG C of roastings 4h, 20%H2-N2Mixed gas After the lower 350 DEG C of reduction 1h of atmosphere, that is, obtain methanation Ni/ZrO2Catalyst.
The Ni/ZrO of preparation2The specific surface area of catalyst is 73.8 m2/ g, aperture is 15.9 nm, and the load capacity of Ni is 8wt%。
CO methanations test result indicate that：Catalyst keeps activity higher in reaction temperature, wherein in reaction temperature The middle CO concentration that can make to work off one's feeling vent one's spleen between 210 ~ 330 DEG C of degree is down to below 10ppm, and keeps selectivity to be not less than 50%.
Embodiment 4
（1）By ZrCl4, BDC and DMF is with mol ratio 1:1:After 400 uniform mixing, 120 DEG C of h of crystallization 72, centrifugation, successively Washed with DMF and methyl alcohol three times, 65 DEG C of drying obtain white powder；The white powder that will be obtained is soaked three days with methanol solvate, And methyl alcohol is changed daily, the part and solvent molecule that will be remained in sample are cemented out, and the white powder of last gained is in 65 DEG C Dry, obtain metal-organic framework materials Zr-MOF；
（2）8 ml concentration are taken for 0.06 g/ml NiCl2·6H2The aqueous solution of O, after being stirring evenly and then adding into 0.2 g pretreatments Zr-MOF, the at room temperature h of high degree of agitation 12, after centrifugation, 65 DEG C of dryings in Muffle furnace 400 DEG C of roastings 3h, 20% H2-N2Mixing After the lower 350 DEG C of reductase 12 h of gas atmosphere, that is, obtain methanation Ni/ZrO2Catalyst.
The Ni/ZrO of preparation2The specific surface area of catalyst is 88 m2/ g, aperture is 9.0 nm, and the load capacity of Ni is 15 wt%。
CO methanations test result indicate that：Catalyst keeps activity higher in reaction temperature, wherein in reaction temperature The middle CO concentration that can make to work off one's feeling vent one's spleen between 240 ~ 340 DEG C of degree is down to below 10ppm, and keeps selectivity to be not less than 50%.
Embodiment 5
（1）By ZrCl4, BDC and DMF is with mol ratio 1:1:After 500 uniform mixing, 125 DEG C of h of crystallization 24, centrifugation, successively Washed with DMF and methyl alcohol three times, 65 DEG C of drying obtain white powder；The white powder that will be obtained is soaked three days with methanol solvate, And methyl alcohol is changed daily, the part and solvent molecule that will be remained in sample are cemented out, and the white powder of last gained is in 65 DEG C Dry, obtain metal-organic framework materials Zr-MOF；
（2）8ml concentration is taken for 0.012 g/ml NiCl2·6H2The ethanol solution of O, is stirring evenly and then adding into 0.2 g pretreatments Zr-MOF afterwards, the at room temperature h of high degree of agitation 24, after centrifugation, 75 DEG C of dryings in Muffle furnace 450 DEG C of roastings 3 h, 20%H2/N2Gas After 1.5 h of the lower 400 DEG C of reduction of atmosphere, that is, obtain methanation Ni/ZrO2Catalyst.
Prepare Ni/ZrO2Specific surface area of catalyst be 84.0 m2/ g, aperture is 9.7 nm, and the load capacity of Ni is 10wt%.
Ni/ZrO manufactured in the present embodiment2The CO exit concentrations and CH of catalyst4Exit concentration vary with temperature such as Fig. 8 a and Shown in Fig. 8 b, it can be seen that catalyst keeps activity higher in reaction temperature, wherein in reaction temperature 210- In the range of 280 DEG C, the middle CO concentration that can make to work off one's feeling vent one's spleen is down to below 10ppm, while keeping CH4Concentration is less than 2%, i.e., selectively More than 50%.

Claims (8)

1. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures2Catalyst, it is characterised in that main active component is Ni, carrier is ZrO2；The specific surface area of catalyst is 55 ~ 98 m2/ g, aperture is 9.0 ~ 16.2 nm, and the load capacity of Ni is 5 ~ 15 wt%。
2. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures described in claim 12The preparation side of catalyst Method, it is characterised in that comprise the following steps：
（1）The preparation of metal-organic framework materials Zr-MOF：By ZrCl4, terephthalic acid (TPA) and dimethylformamide uniformly mix, Thermostatic crystallization；Crystal is washed after drying through dimethylformamide, methyl alcohol, and again with methanol immersion, centrifugation obtains white powder after drying End, i.e., described metal-organic framework materials Zr-MOF；
（2）Ni/ZrO2The preparation of catalyst：Obtained metal-organic framework materials Zr-MOF is added to NiCl2·6H2O is molten Impregnated in liquid, and stirred at room temperature, be centrifuged, dried, roasting, reduction obtains the Ni/ZrO2Catalyst.
3. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures according to claim 22The preparation of catalyst Method, it is characterised in that step（1）In, the ZrCl4, terephthalic acid (TPA) and dimethylformamide mol ratio be 1:1:150 ~500。
4. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures according to claim 22The preparation of catalyst Method, it is characterised in that step（1）In, the temperature of the crystallization is 110 ~ 130 DEG C, and the time of crystallization is 24 ~ 72 h.
5. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures according to claim 22The preparation of catalyst Method, it is characterised in that step（1）In, the time of the methyl alcohol immersion is 3 ~ 5 days, and the methyl alcohol for more renewing daily；It is described dry Dry temperature is 65 ~ 75 DEG C.
6. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures according to claim 22The preparation of catalyst Method, it is characterised in that step（2）In, metal-organic framework materials Zr-MOF and NiCl2·6H2O is in unit volume solution Quality proportioning be 1:0.024~2.4；NiCl2·6H2The solvent of O solution is water or ethanol；Metal-organic framework materials Zr- MOF is in NiCl2·6H2The time stirred in O solution is 5 ~ 24 h；The dry temperature is 65 ~ 75 DEG C.
7. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures according to claim 22The preparation of catalyst Method, it is characterised in that step（2）In, the roasting is to be calcined in air atmosphere, and the temperature of roasting is 400 ~ 550 DEG C, roasting The time of burning is 2 ~ 4 h.
8. a kind of CO selective methanations Ni/ZrO based on Zr-MOF structures according to claim 22The preparation of catalyst Method, it is characterised in that step（2）In, the atmosphere of the reduction is 20vol%H2-N2Gaseous mixture atmosphere, the temperature of reduction is 350 ~ 450 DEG C, the time of reduction is 1 ~ 2h.
CN201710008930.5A 2017-01-06 2017-01-06 A kind of CO selective methanations Ni/ZrO based on Zr MOF structures2Catalyst and preparation method thereof Pending CN106784895A (en)

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CN108428906A (en) * 2018-04-11 2018-08-21 武汉理工大学 It is a kind of using MOF as the preparation method of the low Pt carrying capacity fuel-cell catalyst of template
CN108607611A (en) * 2018-04-19 2018-10-02 上海理工大学 A kind of Cu-Ce-Zr mixed metal oxide catalysts
CN109103464A (en) * 2018-08-30 2018-12-28 广州大学 A kind of preparation method of Catalytic Layer, Catalytic Layer and microbiological fuel cell
CN110437800A (en) * 2019-07-08 2019-11-12 山东大学 ZrO derived from a kind of Co modified metal organic frame2/ C electromagnetic wave absorbent material and the preparation method and application thereof
CN110479280A (en) * 2019-07-17 2019-11-22 华南理工大学 A kind of CO cryogenic selective methanation Ni-ZrO2/NiAl2O4Catalyst and its preparation method and application
CN110661008A (en) * 2019-10-11 2020-01-07 南京航空航天大学 Double-metal-activity monatomic catalyst for metal-air battery, preparation method of monatomic catalyst and metal-air battery
CN111054443A (en) * 2019-12-26 2020-04-24 华南理工大学 Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof
CN112979969A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Multilevel morphology metal-organic framework material, preparation method and application thereof
CN113457681A (en) * 2021-07-08 2021-10-01 上海纳米技术及应用国家工程研究中心有限公司 MOFs-derived Co-based catalyst for catalytic combustion of non-methane total hydrocarbons and preparation method and application thereof
WO2021202565A1 (en) * 2020-03-31 2021-10-07 Numat Technologies Inc. Modified metal-organic framework (mof) compositions, process of making and process of use thereof
CN115582147A (en) * 2022-10-26 2023-01-10 曲阜师范大学 Catalyst and preparation method and application thereof
US11958034B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Activated amino containing metal organic framework (MOF) compositions, process of making and process of use thereof

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CN107233924A (en) * 2017-07-14 2017-10-10 福州大学 The preparation and application of the metal organic framework compound catalyst of sulfydryl modification
CN108428906A (en) * 2018-04-11 2018-08-21 武汉理工大学 It is a kind of using MOF as the preparation method of the low Pt carrying capacity fuel-cell catalyst of template
CN108428906B (en) * 2018-04-11 2020-10-16 武汉理工大学 Preparation method of low-Pt-loading fuel cell catalyst with MOF as template
CN108607611A (en) * 2018-04-19 2018-10-02 上海理工大学 A kind of Cu-Ce-Zr mixed metal oxide catalysts
CN109103464A (en) * 2018-08-30 2018-12-28 广州大学 A kind of preparation method of Catalytic Layer, Catalytic Layer and microbiological fuel cell
CN110437800B (en) * 2019-07-08 2020-07-17 山东大学 Co/ZrO2/C electromagnetic wave absorbing material and preparation method and application thereof
CN110437800A (en) * 2019-07-08 2019-11-12 山东大学 ZrO derived from a kind of Co modified metal organic frame2/ C electromagnetic wave absorbent material and the preparation method and application thereof
CN110479280A (en) * 2019-07-17 2019-11-22 华南理工大学 A kind of CO cryogenic selective methanation Ni-ZrO2/NiAl2O4Catalyst and its preparation method and application
CN110661008A (en) * 2019-10-11 2020-01-07 南京航空航天大学 Double-metal-activity monatomic catalyst for metal-air battery, preparation method of monatomic catalyst and metal-air battery
CN112979969A (en) * 2019-12-12 2021-06-18 中国科学院大连化学物理研究所 Multilevel morphology metal-organic framework material, preparation method and application thereof
CN112979969B (en) * 2019-12-12 2022-04-15 中国科学院大连化学物理研究所 Multilevel morphology metal-organic framework material, preparation method and application thereof
CN111054443A (en) * 2019-12-26 2020-04-24 华南理工大学 Zirconium-based MOF catalyst loaded with double active sites and preparation method and application thereof
WO2021202565A1 (en) * 2020-03-31 2021-10-07 Numat Technologies Inc. Modified metal-organic framework (mof) compositions, process of making and process of use thereof
US11958033B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Modified metal-organic framework (MOF) compositions, process of making and process of use thereof
US11958034B2 (en) 2020-03-31 2024-04-16 Numat Technologies, Inc. Activated amino containing metal organic framework (MOF) compositions, process of making and process of use thereof
CN113457681A (en) * 2021-07-08 2021-10-01 上海纳米技术及应用国家工程研究中心有限公司 MOFs-derived Co-based catalyst for catalytic combustion of non-methane total hydrocarbons and preparation method and application thereof
CN113457681B (en) * 2021-07-08 2022-12-27 上海纳米技术及应用国家工程研究中心有限公司 MOFs-derived Co-based catalyst for catalytic combustion of non-methane total hydrocarbons and preparation method and application thereof
CN115582147A (en) * 2022-10-26 2023-01-10 曲阜师范大学 Catalyst and preparation method and application thereof

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