CN112452347A - Preparation method and application of 2D-RNPG @ CoxOy composite material - Google Patents
Preparation method and application of 2D-RNPG @ CoxOy composite material Download PDFInfo
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- CN112452347A CN112452347A CN202011123185.7A CN202011123185A CN112452347A CN 112452347 A CN112452347 A CN 112452347A CN 202011123185 A CN202011123185 A CN 202011123185A CN 112452347 A CN112452347 A CN 112452347A
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 31
- 239000001257 hydrogen Substances 0.000 claims abstract description 28
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 19
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 10
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 9
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 9
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 230000002153 concerted effect Effects 0.000 claims abstract description 3
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 23
- 239000000243 solution Substances 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000010992 reflux Methods 0.000 claims description 8
- GCQAIVVOMYMPIT-UHFFFAOYSA-N O.O.O.O.O.O.O.O.C1(CCCCCCCCCCCCCCC1)=O Chemical compound O.O.O.O.O.O.O.O.C1(CCCCCCCCCCCCCCC1)=O GCQAIVVOMYMPIT-UHFFFAOYSA-N 0.000 claims description 7
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- 229910021389 graphene Inorganic materials 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- BZDGCIJWPWHAOF-UHFFFAOYSA-N benzene-1,2,4,5-tetramine;hydron;tetrachloride Chemical compound Cl.Cl.Cl.Cl.NC1=CC(N)=C(N)C=C1N BZDGCIJWPWHAOF-UHFFFAOYSA-N 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000004689 octahydrates Chemical class 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 2
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 229910000510 noble metal Inorganic materials 0.000 abstract description 7
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000005457 ice water Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000001228 spectrum Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005286 illumination Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000000944 Soxhlet extraction Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 238000005086 pumping Methods 0.000 description 3
- 238000010791 quenching Methods 0.000 description 3
- 230000000171 quenching effect Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- -1 tetraaminobenzene tetrahydrate Chemical class 0.000 description 3
- 238000001514 detection method Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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Abstract
The invention discloses a preparation method and application of a 2D-RNPG @ CoxOy composite material, and the 2D-RNPG @ CoxOy two-dimensional composite material is prepared by encapsulating multi-valence cobalt oxide nanoparticles in two-dimensional RNPG through in-situ polymerization. The composite material shows excellent photo-thermal concerted catalysis performance on the decomposition of sodium borohydride to produce hydrogen in an alkaline aqueous solution. Due to strong interaction between the multivalent cobalt oxide nanoparticles and the RNPG framework, the catalyst has higher catalytic activity and stability; the raw materials used in the synthesis process have low cost and are expected to replace noble metal catalysts.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a preparation method and application of a 2D-RNPG @ CoxOy composite material, in particular to a preparation method and application of a multivalent cobalt oxide/RNPG/two-dimensional composite material (2D-RNPG @ CoxOy).
Background
Hydrogen is a highly efficient renewable clean energy source and is a substitute for traditional fossil energy sources. The problem facing hydrogen energy applications is storage and release. The mass hydrogen storage density and the volume hydrogen storage density of sodium borohydride exceed those of the traditional hydrogen storage materials, but the sodium borohydride has poor dynamic performance and generates impurity gas in the hydrogen release process, and a catalyst is needed to ensure the efficient release of hydrogen. The catalysts used at present are basically noble metal catalysts with high cost, so that the development of non-noble metal catalysts with low cost is necessary to promote the application of hydrogen storage and release of sodium borohydride.
In recent years, heteroatom-rich microporous graphene or graphene porous polymer nanosheets have been widely researched in the field of hydrogen production by catalytic decomposition of sodium borohydride. Due to the ordered micro-channels, large surface area and large pore volume, the method has great potential in the fields of catalysis, gas separation, energy conversion, energy storage, optoelectronics and the like. The cobalt oxide is a promising non-noble metal hydrogen production catalyst, the cobalt oxide catalyst compounded with the two-dimensional network polymer has good crystallinity, and the catalyst has higher catalytic activity and stability due to strong interaction between the multi-valence cobalt oxide nanoparticles and the RNPG framework; the raw materials used in the synthesis process have low cost and are expected to replace noble metal catalysts.
Disclosure of Invention
The invention provides a preparation method and application of a 2D-RNPG @ CoxOy composite material, which comprises the steps of carrying out in-situ solvothermal synthesis on an encapsulated cobalt oxide (RNPG @ CoxOy), and carrying out in-situ solvothermal synthesis on 2D-RNPG @ CoxOy to alkaline sodium borohydride (NaBH)4) Hydrolysis of the solution to produce hydrogen (H)2) The catalyst has excellent catalytic activity, and the maximum hydrogen production rate is equivalent to that of a catalyst containing other noble metals in an alkaline solution.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a 2D-RNPG @ CoxOy composite material takes a nitrogen-rich graphene porous conjugated network polymer (RNPG) as a carrier, and oxides of multivalent cobalt are loaded on the surface of the RNPG.
Preferably, the preparation method of the 2D-RNPG @ CoxOy composite material comprises the following steps: anhydrous cobalt chloride (CoCl)2) Under the existing condition, concentrated sulfuric acid is used as a catalyst, 1,2,4, 5-tetraaminobenzene tetrahydrochloride and cyclohexadene octahydrate are polymerized in an N-methyl-2-pyrrolidone (NMP) solution for 6 to 10 hours at the temperature of 160-200 ℃; and then adding sodium borohydride for reduction, continuously refluxing for 6-10h, filtering the product, drying, grinding and roasting to obtain the 2D-RNPG @ CoxOy composite material.
Preferably, the weight ratio of the 1,2,4, 5-tetraaminobenzene tetrahydrochloride to the cyclohexadecanone octahydrate is 1:1-3:2, and the weight ratio of the cyclohexadecanone octahydrate to the anhydrous cobalt chloride is 1:1-2: 3.
Preferably, the roasting temperature is 400-500 ℃, and the roasting time is 2-4 h.
An application of a 2D-RNPG @ CoxOy composite material is applied to a photo-thermal concerted catalysis process.
Preferably, the method is applied to hydrogen production by catalyzing the decomposition of the sodium borohydride solution under the condition of the sodium hydroxide solution.
Preferably, the mass fraction of the sodium hydroxide aqueous solution is 3-5%, and the mass fraction of the sodium borohydride aqueous solution is 1-2%.
Compared with the prior art, the invention has the beneficial effects that: 1. preparing a 2D-RNPG @ CoxOy composite material by using a simple in-situ solvent thermal synthesis method; 2. the raw materials used in the synthesis process have low cost and are expected to replace noble metal catalysts; 3. due to the strong interaction between the cobalt oxide nanoparticles and the nitrogen-rich graphene porous conjugated network polymer (RNPG) skeleton, the catalyst has high catalytic activity and stability.
Drawings
FIG. 1 is a structural formula of a basal plane repeating unit of a 2D-RNPG @ CoxOy composite material of the present invention;
FIG. 2 is an XPS test spectrum of a 2D-RNPG @ CoxOy composite of the present invention;
FIG. 3 is a XPS test C spectrum of a 2D-RNPG @ CoxOy composite of the present invention;
FIG. 4 is an XPS test N spectrum of a 2D-RNPG @ CoxOy composite of the present invention;
FIG. 5 is a Fourier infrared spectrum of a 2D-RNPG @ CoxOy composite material of the present invention;
FIG. 6 is a graph of temperature versus hydrogen production for a 2D-RNPG @ CoxOy composite of the present invention as a catalyst;
FIG. 7 is a graph showing the relationship between the temperature of a catalyst and the hydrogen production per unit time, wherein the catalyst is a 2D-RNPG @ CoxOy composite material.
FIG. 8 is a graph comparing the hydrogen production per minute per unit catalyst (1g) in the absence of light at 6 ℃ and under 100W LED light for a 2D-RNPG @ CoxOy composite of the present invention as a catalyst.
FIG. 9 is a graph showing a comparison of hydrogen production per minute per unit catalyst (1g) under a CEL-M500/300 mercury lamp light source without light at 50 ℃ in the presence of a 2D-RNPG @ CoxOy composite of the present invention as a catalyst.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows:
a preparation method of a 2D-RNPG @ CoxOy composite material comprises the following steps:
(a) 0.5751g (2.02mmol) of tetraaminobenzene tetrahydrate, 0.4214g (1.35mmol) of cyclohexadecanone octahydrate and 0.2876g (2.02mmol) of anhydrous cobalt chloride are weighed into a three-neck flask, vacuum pumping and nitrogen atmosphere are carried out, 30mL of anhydrous N-methylpyrrolidone (NMP) is added under the condition of ice water bath, oil bath is dissolved for about 1h at 100 ℃, and the mixture is cooled to room temperature;
(b) transferring into ice water bath, slowly dropwise adding 0.5ml concentrated sulfuric acid, continuing stirring for 1h, transferring to 180 deg.C oil bath for refluxing for 8h, and turning off heating and cooling to room temperature;
(c) transferring into ice water bath, and slowly dropwise adding 10% NaBH4Continuously refluxing 10mL of NMP solution at 180 ℃ for 8h, closing, heating and cooling to room temperature, quenching with 100mL of water, performing suction filtration to obtain a crude product, and performing Soxhlet extraction with water and methanol for 24h to remove impurities;
(d) the resulting product was freeze-dried using a freeze dryer and, after grinding, was purified at N2Roasting for 3h at 450 ℃ in the atmosphere to obtain the 2D-RNPG @ CoxOy composite material.
Example two:
a preparation method of a 2D-RNPG @ CoxOy composite material comprises the following steps:
(a) 0.5751g (2.02mmol) of tetraaminobenzene tetrahydrate, 0.4214g (1.35mmol) of cyclohexadecanone octahydrate and 0.2876g (2.02mmol) of anhydrous cobalt chloride are weighed into a three-neck flask, vacuum pumping and nitrogen atmosphere are carried out, 30mL of anhydrous N-methylpyrrolidone (NMP) is added under the condition of ice water bath, oil bath is carried out for dissolving at 90 ℃ for about 1.5h, and cooling is carried out to room temperature;
(b) transferring into ice water bath, slowly dropwise adding 0.5ml concentrated sulfuric acid, continuing stirring for 0.8h, transferring to 160 ℃ oil bath for refluxing for 10h, and turning off heating and cooling to room temperature;
(c) transferring into ice water bath, and slowly dropwise adding 10% NaBH4Continuously refluxing 10mL of NMP solution at 200 ℃ for 6h, closing, heating and cooling to room temperature, quenching with 100mL of water, performing suction filtration to obtain a crude product, and performing Soxhlet extraction with water and methanol for 20h to remove impurities;
(d) the resulting product was freeze-dried using a freeze dryer and, after grinding, was purified at N2And roasting at 400 ℃ for 4h in the atmosphere to obtain the 2D-RNPG @ CoxOy composite material.
Example three:
a preparation method of a 2D-RNPG @ CoxOy composite material comprises the following steps:
(a) 0.5751g (2.02mmol) of tetraaminobenzene tetrahydrate, 0.4214g (1.35mmol) of cyclohexadecanone octahydrate and 0.2876g (2.02mmol) of anhydrous cobalt chloride are weighed into a three-neck flask, vacuum pumping and nitrogen atmosphere are carried out, 30mL of anhydrous N-methylpyrrolidone (NMP) is added under the condition of ice water bath, oil bath is dissolved for about 0.8h at 120 ℃, and the mixture is cooled to room temperature;
(b) transferring into ice water bath, slowly dropwise adding 0.5ml concentrated sulfuric acid, continuing stirring for 1.2h, transferring to 200 deg.C oil bath for refluxing for 6h, and turning off heating and cooling to room temperature;
(c) transferring into ice water bath, and slowly dropwise adding 10% NaBH4Continuously refluxing 10mL of NMP solution at 160 ℃ for 10h, closing, heating and cooling to room temperature, quenching 100mL of water for reaction, performing suction filtration to obtain a crude product, and performing Soxhlet extraction for 26h by using water and methanol respectively to remove impurities;
(d) the resulting product was freeze-dried using a freeze dryer and, after grinding, was purified at N2And roasting at 500 ℃ for 2h in the atmosphere to obtain the 2D-RNPG @ CoxOy composite material.
Test examples
The catalytic hydrogen production test was carried out on a CEL-SPH2N test platform (beijing zhongzhijin source limited) equipped with an automatic gas chromatograph, and the reaction vessel was made of heat-resistant quartz glass and kept in vacuum with a vacuum pump at a capacity of 150 mL. The detection of the gas phase products was carried out using an on-line gas chromatograph (Shimadzu GC-8A) and a5A molecular sieve column equipped with a thermal conductivity detector (GC-TCD, detection H)2And O2The carrier gases are nitrogen and helium, respectively).
FIG. 2 is an XPS test spectrum, a full XPS test spectrum, with an inset showing linear peaks of Co element, indicating that the oxidation state of Co in RNPG @ CoxOy is mainly Co3+State, and Co2+The content is low.
Fig. 3 and 4 show XPS test spectra showing linear peaks of linear C, N elements.
FIG. 5 is a Fourier infrared spectrum, two wide frequency bands 3359, 3214cm-1Resonance from hydroxyl and amino groups, 1620 and 1040cm-1The attribute is aromatic skeleton vibration.
FIG. 6 shows that 5mg of catalyst, 0.3g of sodium borohydride and 1g of sodium hydroxide are injected with 30mL of water, the hydrogen production rate of the unit catalyst changes with time under different temperature conditions, the catalytic hydrogen production rate is continuously improved along with the continuous rise of the temperature, the catalytic performance at 45 ℃ is the best, the hydrogen production rate is the highest and reaches 103759.3mLg-1。
FIG. 7 shows the hydrogen production per minute of a single catalyst at different temperatures in the case of 5mg of catalyst, 0.3g of sodium borohydride and 1g of sodium hydroxide injected with 30mL of water, and the best catalytic performance is obtained at 45 ℃ as well,the highest hydrogen production rate reaches 1152.8mL g-1·min-1。
FIG. 8 shows hydrogen production per minute of a single catalyst at 6 ℃ without illumination and 100W LED illumination by injecting 30mL of water into 5mg of catalyst, 0.3g of sodium borohydride and 1g of sodium hydroxide, and it can be seen that the hydrogen production under LED illumination is significantly better than that under a light-shielding condition, and a good photo-thermal synergistic effect is exhibited.
FIG. 9 shows that 5mg of catalyst, 0.3g of sodium borohydride, and 1g of sodium hydroxide are injected with 30mL of water, the hydrogen production per minute of the single-site catalyst is performed at 50 ℃ without illumination and under the light source of a CEL-M500/300 mercury lamp, and the catalytic effect under the mercury lamp condition is obviously better than that under the dark condition at the same temperature of 50 ℃, and the good photo-thermal synergistic effect is exhibited.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. The preparation method of the 2D-RNPG @ CoxOy composite material is characterized in that nitrogen-rich graphene porous conjugated network polymer (RNPG) is used as a carrier, and multivalent cobalt oxide is loaded on the surface of the RNPG.
2. The method for preparing the 2D-RNPG @ CoxOy composite material according to claim 1, comprising the following steps:
in anhydrous cobalt chloride (CoCl)2) Under the existing condition, concentrated sulfuric acid is used as a catalyst, 1,2,4, 5-tetraaminobenzene tetrahydrochloride and cyclohexadene octahydrate are polymerized in an N-methyl-2-pyrrolidone (NMP) solution for 6 to 10 hours at the temperature of 160-200 ℃; and then adding sodium borohydride for reduction, continuously refluxing for 6-10h, filtering the product, drying, grinding and roasting to obtain the 2D-RNPG @ CoxOy composite material.
3. The preparation method of the 2D-RNPG @ CoxOy composite material as claimed in claim 2, wherein the weight ratio of 1,2,4, 5-tetraaminobenzene tetrahydrochloride to cyclohexadecanone octahydrate is 1:1-3:2, and the weight ratio of cyclohexadecanone octahydrate to anhydrous cobalt chloride is 1:1-2: 3.
4. The method as claimed in claim 2, wherein the calcination temperature is 400-500 ℃ and the calcination time is 2-4 h.
5. Use of a 2D-RNPG @ CoxOy composite material according to any of claims 1-4 in a photothermal co-catalytic process.
6. The application of the 2D-RNPG @ CoxOy composite material as claimed in claim 5, which is applied to the photo-thermal concerted catalysis of the decomposition of sodium borohydride solution to produce hydrogen under the condition of sodium hydroxide aqueous solution.
7. The use of the 2D-RNPG @ CoxOy composite material as claimed in claim 6, wherein the mass fraction of the aqueous sodium hydroxide solution is 3-5% and the mass fraction of the aqueous sodium borohydride solution is 1-2%.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150224484A1 (en) * | 2014-02-13 | 2015-08-13 | Postech Academy-Industry Foundation | Inorganic Nanoparticle Deposited Catalyst For Hydrogenation And Manufacturing Method Of The Same, And Hydrogenation For Biomass Derived Hydrocarbon Compounds |
| CN107433205A (en) * | 2016-05-25 | 2017-12-05 | 中国科学院大连化学物理研究所 | Covalent organic frame load cobalt catalyst and its preparation and application |
| CN108927224A (en) * | 2018-06-28 | 2018-12-04 | 福州大学 | A kind of covalent organic frame catalysis material and its preparation method and application of cobalt ions load |
| US20200247668A1 (en) * | 2016-12-02 | 2020-08-06 | Council Of Scientific & Industrial Research | Photo-catalytic splitting of water using self-assembled metalloporphyrin 2d-sheets |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150224484A1 (en) * | 2014-02-13 | 2015-08-13 | Postech Academy-Industry Foundation | Inorganic Nanoparticle Deposited Catalyst For Hydrogenation And Manufacturing Method Of The Same, And Hydrogenation For Biomass Derived Hydrocarbon Compounds |
| CN107433205A (en) * | 2016-05-25 | 2017-12-05 | 中国科学院大连化学物理研究所 | Covalent organic frame load cobalt catalyst and its preparation and application |
| US20200247668A1 (en) * | 2016-12-02 | 2020-08-06 | Council Of Scientific & Industrial Research | Photo-catalytic splitting of water using self-assembled metalloporphyrin 2d-sheets |
| CN108927224A (en) * | 2018-06-28 | 2018-12-04 | 福州大学 | A kind of covalent organic frame catalysis material and its preparation method and application of cobalt ions load |
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