CN111151305B - Copper doped ultra-thin TiO2Application of nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production - Google Patents
Copper doped ultra-thin TiO2Application of nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production Download PDFInfo
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- 239000010941 cobalt Substances 0.000 title claims abstract description 31
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 31
- -1 cobalt oxime Chemical class 0.000 title claims abstract description 30
- 239000002135 nanosheet Substances 0.000 title claims abstract description 30
- 239000001257 hydrogen Substances 0.000 title claims abstract description 27
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 239000010949 copper Substances 0.000 title claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 12
- 229910052802 copper Inorganic materials 0.000 title claims description 12
- 230000001699 photocatalysis Effects 0.000 title abstract description 12
- 238000000354 decomposition reaction Methods 0.000 title abstract description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 18
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 17
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 6
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 3
- 238000010926 purge Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- 238000002360 preparation method Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 6
- TWBYWOBDOCUKOW-UHFFFAOYSA-N isonicotinic acid Chemical compound OC(=O)C1=CC=NC=C1 TWBYWOBDOCUKOW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000047 product Substances 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 4
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 claims description 3
- JGUQDUKBUKFFRO-CIIODKQPSA-N dimethylglyoxime Chemical compound O/N=C(/C)\C(\C)=N\O JGUQDUKBUKFFRO-CIIODKQPSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 239000012065 filter cake Substances 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 description 13
- 238000010586 diagram Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000003278 mimic effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000011715 vitamin B12 Substances 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- 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
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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
- C01B3/042—Decomposition of water
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
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- B01J2540/00—Compositional aspects of coordination complexes or ligands in catalyst systems
- B01J2540/10—Non-coordinating groups comprising only oxygen beside carbon or hydrogen
- B01J2540/12—Carboxylic acid groups
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Abstract
The invention relates to copper-doped ultrathin TiO2Application of nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production. Ultrasonically dispersing a catalyst in glycerol aqueous solution, vacuumizing a reaction system, purging with nitrogen to remove oxygen, and carrying out catalytic reaction under sunlight; the catalyst is copper-doped ultrathin TiO2The nanosheet supports the cobalt oxime complex. The invention mixes the cobalt oxime complex containing carboxyl with copper-doped ultrathin TiO2The nano sheets are compounded to prepare a compound Cu-TiO with good photocatalytic activity2-Co. The compound can realize high-efficiency catalytic water decomposition hydrogen production under sunlight.
Description
Technical Field
The invention belongs to the field of catalytic hydrogen production, and particularly relates to copper-doped ultrathin TiO2The nanosheet-loaded cobalt oxime complex is applied to hydrogen production through catalytic water decomposition.
Background
In the field of new energy, hydrogen energy has been widely recognized as an ideal pollution-free green energy source in the new century. Hydrogen is the most abundant element in nature and is widely found in water, fossil fuels, and various types of carbohydrates. However, the traditional hydrogen production method needs to consume huge conventional energy, so that the hydrogen energy price is too high, and the popularization and application of the hydrogen energy are greatly limited. Scientists would then quickly want to utilize inexhaustible, inexpensive solar energy asThe primary energy in the hydrogen energy forming process enables the development of hydrogen energy to show wider prospects. The metal cobalt oxime complex was originally used as vitamin B12The mimic of (2) is attracting attention, and has a high catalytic activity in the field of photocatalysis.
Disclosure of Invention
The invention aims to utilize a carboxyl-containing cobalt oxime complex to be immobilized on copper-doped ultrathin TiO2Nanosheet to obtain copper-doped ultrathin TiO2The nanosheet supports the cobalt oxime complex. The material has good application prospect in catalyzing water to decompose and prepare hydrogen.
In order to achieve the purpose, the invention adopts the technical scheme that: copper doped ultra-thin TiO2The application of the nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production comprises the following steps: ultrasonically dispersing a catalyst in glycerol aqueous solution, vacuumizing a reaction system, purging with nitrogen to remove oxygen, and carrying out catalytic reaction under sunlight; the catalyst is copper-doped ultrathin TiO2The nanosheet supports the cobalt oxime complex.
Preferably, the application is the copper-doped ultrathin TiO2The preparation method of the nanosheet supported cobalt oxime complex comprises the following steps: dissolving a proper amount of carboxyl-containing cobalt oxime complex in absolute ethyl alcohol, and adding a proper amount of copper-doped ultrathin TiO2And (3) dispersing the nanosheets by ultrasonic, stirring for 24-25h at normal temperature, filtering, washing filter cakes by absolute ethyl alcohol, and drying in vacuum to obtain a target product.
Preferably, the above applications, in terms of the ratio of the amounts of the substances, cobalt oxime complex Cu to TiO2＝3:3:94。
Preferably, in the above-mentioned use, the cobalt oxime complex having a carboxyl group is Co (dmgH)2(4-COOH-py) Cl, the preparation method comprises the following steps: adding CoCl2·6H2Dissolving dimethylglyoxime and sodium hydroxide in 95% ethanol, heating to 70 ℃, adding isonicotinic acid, cooling the obtained solution to room temperature, introducing air flow into the solution for 30min to precipitate, filtering, washing the solid with water and ethanol, and drying to obtain the product.
Preferably, the above-mentioned application, the copper dopingHybrid ultra-thin TiO2The preparation method of the nanosheet comprises the following steps: tetrabutyl titanate, hydrofluoric acid and Cu (NO)3)2·3H2Adding O into absolute ethyl alcohol, stirring at room temperature for 30 minutes, transferring to a hydrothermal kettle, heating at 180 ℃ for 2-3 hours, centrifuging, washing the solid with distilled water, and drying at 60 ℃ in vacuum to obtain copper-doped ultrathin TiO2Nanosheets.
Preferably, in the above application, the volume percentage of the glycerol aqueous solution is 5-10%.
The invention has the beneficial effects that: the invention mixes the cobalt oxime complex containing carboxyl with copper-doped ultrathin TiO2The nano sheets are compounded to prepare a compound Cu-TiO with good photocatalytic activity2-Co. The compound can realize high-efficiency catalytic water decomposition hydrogen production under sunlight.
Drawings
FIG. 1 shows a cobalt oxime complex Co (dmgH)2A structural schematic diagram of (4-COOH-py) Cl.
FIG. 2 is a Cu-TiO complex2-structural schematic of Co.
FIG. 3 is an ultra-thin TiO2Nanosheet, composite Cu-TiO2And composite Cu-TiO2-solid uv-vis diffuse reflectance spectrum of Co.
FIG. 4 is a Cu-TiO composite2Transmission electron micrograph (a) and high-resolution transmission electron micrograph (b) of (c).
FIG. 5 is a Cu-TiO composite2EDX diagram of Co.
FIG. 6 is a Cu-TiO composite2Schematic diagram of hydrogen production by photocatalytic water splitting of Co.
FIG. 7 is a composite TiO2-Co(a)、Cu-TiO2(b) And Cu-TiO2Hydrogen production comparison diagram of Co (c).
Detailed Description
EXAMPLE 1 copper-doped ultrathin TiO2Application of nanosheet-loaded cobalt oxime complex in photocatalytic water decomposition hydrogen production
Copper doped ultrathin TiO2Nanosheet-supported cobalt oxime complex (Cu-TiO)2Preparation of-Co)
1. Ultra-thin TiO 22Preparation of nanosheets
Adding 10mL tetrabutyl titanate and 1.2mL HF into 40mL absolute ethyl alcohol, stirring for 30min, transferring into a hydrothermal kettle, heating at 180 ℃ for 2h, centrifuging, repeatedly washing the solid with distilled water, and finally, vacuum drying at 60 ℃ for 24 h.
2. Copper doped ultra-thin TiO2Nanosheet (Cu-TiO)2) Preparation of
To 40mL of absolute ethanol were added 10mL of tetrabutyl titanate, 1.2mL of HF and 400mg of Cu (NO)3)2·3 H2O, stirring for 30min, transferring to a hydrothermal kettle, heating at 180 ℃ for 2h, centrifuging, and repeatedly washing the solid with distilled water. Finally, vacuum drying is carried out for 24h at 60 ℃.
3. Carboxyl group-containing cobalt oxime complex (Co (dmgH)2Preparation of (4-COOH-py) Cl)
CoCl2·6H2O (476mg, 2mmol), dimethylglyoxime (523mg, 4.5mmol), sodium hydroxide (80 mg, 2mmol) were dissolved in 95% ethanol and heated to 70 ℃ and isonicotinic acid (246mg, 2mmol) was added, the resulting solution was cooled to room temperature, air was passed through the solution for 30min, and a precipitate precipitated out, filtered, the solid was washed with water and ethanol and dried to give 380mg of product in 87% yield. The structural formula is shown in figure 1.
4. Copper doped ultra-thin TiO2Nanosheet-supported cobalt oxime complex (Cu-TiO)2Preparation of-Co)
Taking the copper-doped ultrathin TiO obtained in the step 22Nanosheet (Cu-TiO)2) (50mg), carboxyl group-containing cobalt oxime complex (Co (dmgH) obtained in step 32(4-COOH-py) Cl) (5mg, 0.011mmol), ultrasonically dispersing in 5mL absolute ethyl alcohol, stirring for 24h at room temperature, centrifuging, washing with ethanol until the supernatant is colorless, and vacuum drying to obtain solid 42mg, namely the compound Cu-TiO2-Co, the structural formula is shown in figure 2.
(II) the result of the detection
FIG. 3 is an ultra-thin TiO2Nanosheet, composite Cu-TiO2And composite Cu-TiO2-solid uv-vis diffuse reflectance spectrum of Co. By comparison, it can be confirmed that the doping of copper and the modification of cobalt oxime complex can improve the ultra-thin titanium dioxideThe utilization rate of the nanosheet to sunlight.
FIG. 4 is a Cu-TiO composite2Transmission electron micrograph (a) and high-resolution transmission electron micrograph (b). As can be seen from fig. 4, the titanium dioxide nanosheet is an ultra-thin nanosheet, and the thickness of the nanosheet can be determined by calculation to be about 2.8 nm.
FIG. 5 is a Cu-TiO composite2EDX diagram of Co, it can be seen from FIG. 5 that the composite Cu-TiO of the present invention2The content ratio of the cobalt to the copper to the titanium in the Co is 3:3:94, which proves that the copper is successfully doped into the TiO2In the nano-sheet structure, and the cobalt oxime complex is successfully immobilized on Cu-TiO2And (3) the surface of the nanosheet.
(III) catalytic water decomposition hydrogen production
The method comprises the following steps: the composite Cu-TiO2-Co (50mg) was ultrasonically dispersed in 100mL of a 5% by volume aqueous glycerol solution. The reaction was carried out in a quartz reactor. Before the reaction, the reaction mixture was evacuated for 30 minutes and then purged with nitrogen for 30 minutes to remove oxygen. And reacting for 5 hours under visible light. After the reaction was completed, the discharged gas was analyzed every 1 hour for the product (GC-7900) by gas chromatography. The reaction principle is shown in FIG. 6, and the results are shown in Table 1 and FIG. 7.
TABLE 1Cu-TiO2-Co photocatalytic water splitting hydrogen production reaction
As can be seen from FIG. 7 and Table 1, by comparison, it can be seen that after 5 hours, Cu-TiO2Co has a hydrogen production of 210. mu. mol and is Cu-TiO22.2 times of hydrogen production compared with TiO235 times the hydrogen production of Co. Therefore, the doping of copper and the introduction of the cobalt oxime complex obviously improve the catalytic activity. Composite Cu-TiO2Co has high photocatalytic water splitting hydrogen production activity under sunlight, and has potential application prospect in photocatalytic hydrogen production.
Claims (4)
1. Copper doped ultra-thin TiO2Nanosheet-supported cobalt oxime complex photocatalystThe application of the hydrogen production by decomposing the water is characterized in that the method comprises the following steps: ultrasonically dispersing a catalyst in glycerol aqueous solution, vacuumizing a reaction system, purging with nitrogen to remove oxygen, and carrying out catalytic reaction under sunlight;
the catalyst is copper-doped ultrathin TiO2The preparation method of the nanosheet-supported cobalt oxime complex comprises the following steps: dissolving a proper amount of carboxyl-containing cobalt oxime complex in absolute ethyl alcohol, and adding a proper amount of copper-doped ultrathin TiO2Carrying out ultrasonic dispersion on the nanosheets, stirring for 24-25h at normal temperature, filtering, washing filter cakes by absolute ethyl alcohol, and drying in vacuum to obtain a target product;
the cobalt oxime complex containing a carboxyl group is Co (dmgH)2(4-COOH-py) Cl, the preparation method comprises the following steps: adding CoCl2·6H2Dissolving O, dimethylglyoxime and sodium hydroxide in 95% ethanol, and heating to 70%oAnd C, adding isonicotinic acid, cooling the obtained solution to room temperature, introducing air flow into the solution for 30min, separating out precipitates, filtering, washing solids with water and ethanol, and drying to obtain the product.
2. Use according to claim 1, wherein the ratio of the amounts of the substances is Cu to TiO cobalt oxime complex2= 3 : 3 : 94。
3. Use according to claim 1, characterized in that the copper-doped ultra-thin TiO is2The preparation method of the nanosheet comprises the following steps: tetrabutyl titanate, hydrofluoric acid and Cu (NO)3)2·3H2Adding O into absolute ethyl alcohol, stirring for 30 minutes at room temperature, transferring into a hydrothermal kettle, and stirring 180 DEGoHeating for 2-3h, centrifuging, washing the solid with distilled water, and standing for 60 deg.CoC, vacuum drying to obtain copper-doped ultrathin TiO2Nanosheets.
4. Use according to claim 1, characterized in that the aqueous glycerol solution is present in a percentage of 5-10% by volume.
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| CN105239091A (en) * | 2014-07-10 | 2016-01-13 | 中国科学院理化技术研究所 | Photocathode based on metal oxide, quantum dot and hydrogen production catalyst, and preparation and application thereof |
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