CN110479371A - A kind of preparation method and application of ligand/plant photochemical catalyst - Google Patents
A kind of preparation method and application of ligand/plant photochemical catalyst Download PDFInfo
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- CN110479371A CN110479371A CN201910742369.2A CN201910742369A CN110479371A CN 110479371 A CN110479371 A CN 110479371A CN 201910742369 A CN201910742369 A CN 201910742369A CN 110479371 A CN110479371 A CN 110479371A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- 239000003446 ligand Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 230000001699 photocatalysis Effects 0.000 claims abstract description 20
- 238000010531 catalytic reduction reaction Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 241000196324 Embryophyta Species 0.000 claims description 108
- 240000000111 Saccharum officinarum Species 0.000 claims description 40
- 235000007201 Saccharum officinarum Nutrition 0.000 claims description 40
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 240000008042 Zea mays Species 0.000 claims description 7
- 235000016383 Zea mays subsp huehuetenangensis Nutrition 0.000 claims description 7
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 7
- 235000009973 maize Nutrition 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 241001143500 Aceraceae Species 0.000 claims description 4
- 241000209504 Poaceae Species 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- 241000208140 Acer Species 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 104
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 21
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- VFLDPWHFBUODDF-FCXRPNKRSA-N curcumin Chemical compound C1=C(O)C(OC)=CC(\C=C\C(=O)CC(=O)\C=C\C=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-FCXRPNKRSA-N 0.000 description 8
- 235000014676 Phragmites communis Nutrition 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 241000510091 Quadrula quadrula Species 0.000 description 5
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000004148 curcumin Substances 0.000 description 4
- 235000012754 curcumin Nutrition 0.000 description 4
- 229940109262 curcumin Drugs 0.000 description 4
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 244000017020 Ipomoea batatas Species 0.000 description 3
- 235000002678 Ipomoea batatas Nutrition 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 239000004519 grease Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000003595 mist Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000013177 MIL-101 Substances 0.000 description 1
- 239000013206 MIL-53 Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000013207 UiO-66 Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000013082 iron-based metal-organic framework Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000013384 organic framework Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000013096 zirconium-based metal-organic framework Substances 0.000 description 1
Classifications
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0205—Oxygen-containing compounds comprising carbonyl groups or oxygen-containing derivatives, e.g. acetals, ketals, cyclic peroxides
- B01J31/0208—Ketones or ketals
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0244—Nitrogen containing compounds with nitrogen contained as ring member in aromatic compounds or moieties, e.g. pyridine
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of ligand/plant photochemical catalyst preparation methods and application, belong to photocatalyst technology field.Plant photochemical catalyst is made in plant leaf blade by the present invention；Plant photochemical catalyst, ligand are added in solvent and is 25~180 DEG C, reacts 3d or more under stirring condition in temperature；It is cooled to room temperature, is centrifuged, purifies, being drying to obtain ligand/plant photochemical catalyst.Ligand of the present invention/plant photochemical catalyst possesses good photocatalytic activity under sunlight, can be used for CO2Photo catalytic reduction is at fuel gas CO.
Description
Technical field
The present invention relates to a kind of ligand/plant photochemical catalyst preparation methods and application, belong to photocatalyst technology field.
Background technique
Absorption capture CO2, or by CO2The product (such as methane, alcohols etc.) for being converted into surcharge is to solve CO2It crosses
More important methods.Due to by CO2The product for being converted into added value is by CO2As raw material, it can both reduce CO2Contain
Amount reduces consumption, while can also bring additional economic benefit.It is general in the prior art mainly to use chemistry or biological reducing method also
Former CO2.Due to CO2Molecule is more stable, needs to use high temperature with the reduction of these methods, high pressure is not only at high cost, but also continues
Property is poor, not very practical.Although photocatalysis does not need to carry out by the way of high temperature and pressure, it is only necessary to carry out at typical condition
, economic and environment-friendly, the requirement to equipment and energy input equipment is low, there is very big advantage compared with traditional catalysis process；
But the efficiency of photo catalytic reduction is too low.
Photo catalytic reduction CO2Catalyst be broadly divided into following a few classes: (1) the organic framework of metal (MOF) material, such as Ti-
MOF (MIL-125), Zr-MOF (UiO-66), Fe-MOF (MIL-101, MIL-53) etc.；(2) semiconductor material, such as TiO2,
CdS, g-C3N4And its derivative；(3) other composite materials.Although these photo catalytic reductions CO2Catalyst there is good light to urge
Change activity, but synthesis step is more, prepare it is relative complex, it is at high cost, it is possible to create secondary pollution.Biological template synthesizing flaky is sharp
Titanium ore type titanium dioxide: being template with plant petals, has the titanium dioxide of flake porous type by infusion process preparation.The program
In need to use Butyl Phthalate, belong to toxic and expensive presoma.And Plant Light is prepared currently without the simple ligand of addition and is urged
The report of agent.
Summary of the invention
For photo catalytic reduction CO in the prior art2Catalyst the problem of, provide a kind of ligand/plant photochemical catalyst
Preparation method and application, ligand is added in plant photochemical catalyst in the present invention, has good photocatalytic activity.
A kind of preparation method of ligand/plant photochemical catalyst, the specific steps are as follows:
(1) plant photochemical catalyst is made in plant leaf blade；
(2) step (1) plant photochemical catalyst, ligand are added in solvent and are 25~180 DEG C, stirring condition in temperature
Lower reaction 3d or more；It is cooled to room temperature, is centrifuged, purifies, being drying to obtain ligand/plant photochemical catalyst.
In the step (1) plant leaf blade be made plant photochemical catalyst the specific steps are
1) first plant leaf blade is cleaned, is cut into strip；
2) plant leaf blade cut into inch strips is placed in temperature is 150~280 DEG C of 2~10h of roasting, then be placed in temperature for 300~
500 DEG C of roastings 10~for 24 hours, cool to room temperature with the furnace, then be ground into powder up to plant photochemical catalyst.
Plant leaf blade is Leaf-Blade of Poaceae or Aceraceae plant leaf blade in the step (1).
Preferably, the Leaf-Blade of Poaceae is Sugarcane Leaves, Reed Leaf or maize leaf, Aceraceae plant leaf blade
For maple leaves.
Step (2) ligand is terephthalic acid (TPA) or trimesic acid.
The mass ratio of the plant photochemical catalyst and ligand is (20~1): 1.
Step (2) solvent be N,N-dimethylformamide, methanol, deionized water it is one or more.
The ligand/plant photochemical catalyst is in photo catalytic reduction CO2In application.
Photocatalytic activity evaluation method:
Deionized water and sacrifice is added as reaction light source, catalyst charge 20mg, reaction system in simulated solar irradiation
Agent (TEOA, ascorbic acid or isopropanol), using gas chromatographic detection reaction product CO.
Beneficial effects of the present invention:
(1) ligand of the present invention/plant photochemical catalyst is without toxic presoma, and preparation is simple；
(2) ligand of the present invention/plant photochemical catalyst has efficient photo-catalysis capability, catalyst charge 20mg, CO
Yield can reach 10.39 μm of olg-1·h-1。
Detailed description of the invention
Fig. 1 is that photo catalytic reduction CO after different type ligand is added in sugarcane top photochemical catalyst2When CO yield figure；
Fig. 2 is that photo catalytic reduction CO after terephthalic acid (TPA) is added in different plant photochemical catalysts2When CO yield figure.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
A kind of embodiment 1: preparation method of ligand/plant photochemical catalyst
Terephthalic acid (TPA)/sugarcane top photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (sugarcane top)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
1) first sugarcane top is cleaned, is cut into strip；
2) sugarcane top cut into inch strips is placed in Muffle furnace, roasts 2h at being 280 DEG C in temperature, then in temperature be 460 DEG C
Lower roasting 10h；
3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 107mg plant photochemical catalyst, 65.8mg ligand (terephthalic acid (TPA) H2BDC it is molten) to be added to 50mL
It is 110 DEG C, reacts 3d or more under stirring condition in agent (N,N-dimethylformamide) and in temperature；It is cooled to room temperature, is centrifuged, washes
It washs purifying, be drying to obtain ligand/plant photochemical catalyst；Wherein plant photochemical catalyst and the mass ratio of ligand (terephthalic acid (TPA)) are
107:65.8；
Trimesic acid/sugarcane top photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (sugarcane top)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
1) first sugarcane top is cleaned, is cut into strip；
2) by the sugarcane top cut into inch strips be placed in Muffle furnace be 200 DEG C in temperature at roast 5h, then in the case where temperature is 500 DEG C
Roast 15h；
3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 100mg plant photochemical catalyst, 50mg ligand (trimesic acid H3BTC) it is added to 10mL solvent
It is 90 DEG C, reacts 3d or more under stirring condition in (N,N-dimethylformamide) and in temperature；It is cooled to room temperature, is centrifuged, washs
It purifies, be drying to obtain ligand/plant photochemical catalyst；Wherein plant photochemical catalyst and the mass ratio of ligand (trimesic acid) are
100:50；
Methylimidazole/sugarcane top photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (sugarcane top)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
(1) first sugarcane top is cleaned, is cut into strip；
(2) sugarcane top cut into inch strips is placed in Muffle furnace in temperature is 240 DEG C of roasting 8h, then is 420 DEG C in temperature and roasts
Burn 18h；
(3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 45mg plant photochemical catalyst, 50mg ligand (methylimidazole) be added to 20mL solvent (go from
Sub- water) in and under room temperature, stirring condition react 3d or more；Centrifugation, is drying to obtain ligand/plant photochemical catalyst at washing purifying；
Wherein the mass ratio of plant photochemical catalyst and ligand (methylimidazole) is 45:50；
Curcumin/sugarcane top photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (sugarcane top)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
(1) first sugarcane top is cleaned, is cut into strip；
(2) sugarcane top cut into inch strips is placed in Muffle furnace in temperature is 200 DEG C of roasting 10h, then is 400 DEG C in temperature and roasts
Burn 10h；
(3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 100mg plant photochemical catalyst, 50mg ligand (curcumin) be added to 30mL solvent (N of 10mL,
The deionized water of dinethylformamide, the methanol of 10mL and 10mL) in and temperature be 90 DEG C, under stirring condition reaction 3d with
On；It is cooled to room temperature, is centrifuged, washs purifying, be drying to obtain ligand/plant photochemical catalyst；Wherein plant photochemical catalyst and ligand
The mass ratio of (curcumin) is 100:50；
Ipomoea batatas(L.)Lam/sugarcane top photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (sugarcane top)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
1) first sugarcane top is cleaned, is cut into strip；
2) sugarcane top cut into inch strips is placed in Muffle furnace in temperature is 260 DEG C of roasting 6h, then is 450 DEG C in temperature and roasts
12h；
3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 100mg plant photochemical catalyst, 50mg ligand (trimesic acid H3BTC) it is added to 30mL solvent
It is 90 DEG C, stirring condition in (deionized water of the N,N-dimethylformamide of 10mL, the methanol of 10mL and 10mL) and in temperature
Lower reaction 3d or more；It is cooled to room temperature, is centrifuged, washs purifying, be drying to obtain ligand/plant photochemical catalyst；Wherein Plant Light is urged
The mass ratio of agent and ligand (Ipomoea batatas(L.)Lam) is 100:50；
Ligand/sugarcane top photochemical catalyst photo catalytic reduction CO2:
(1) the 5-50mg catalyst weighed up is added in photo catalysis reactor first, then 0.1-3mL is added wherein
The mixed solution of triethanolamine and 0.1-10mL pure water composition, is constantly stirred later, keeps its evenly dispersed；
(2) appropriate vacuum grease will be coated at ball milling and reactor is fixed on reaction unit.Condensation cycle is opened later
Pump, and it is 5 DEG C that temperature, which is arranged, covers quartz cover after system temperature is stablized；
(3) vacuum pump is opened, the knob on reaction unit is slowly screwed to reactor pressure maintaining from pipeline circulation, system is kept
Evacuated state is constant, this when, system started to vacuumize reactor, and reactor sample introduction is constantly turned in vacuum
Valve prevents dead volume from occurring.Evacuated state keeps 30min or more；
(4) carrier gas and gas-chromatography are opened, is set according to operating condition, is raised to finger to column temperature, detector, reburner
After determining temperature, manual ignition is carried out to chromatography, " water mist " to appear opens acquisition software afterwards, starts to acquire baseline；
(5) knob on reaction unit is screwed at system circulation after vacuumizing, system starts the cycle at this time, at this time
By CO2Gas cylinder is connected at reactor sampling valve, uses CO2Reaction environment is replaced, number is 5-6 times；
(6) reaction unit is got into system circulation by vacuumizing after, keeps 5min；
(7) the CO2 gas of 8mL is squeezed into reaction unit with syringe, later observing response device pressure registration, confirmed
Gas opens jump pump after being successfully entered reaction system, keeps 1h；
(8) light source is opened, frame reacts 4h, take a sample every 1h right above reactor；
Ligand/sugarcane top photochemical catalyst photo catalytic reduction CO2When CO yield figure see Fig. 1, from fig. 1, it can be seen that terephthaldehyde
Acid/sugarcane top photochemical catalyst CO yield has been up to 10.39 μm of olg-1·h-1, hence it is evident that it is urged higher than the light that ligand is not added
Agent, trimesic acid/sugarcane top photochemical catalyst CO yield can achieve 1.46 μm of olg-1·h-1, match also above being not added
The photochemical catalyst of body；And methylimidazole/sugarcane top photochemical catalyst, curcumin/sugarcane top photochemical catalyst and Ipomoea batatas(L.)Lam/sweet
The catalytic activity of sugarcane leaf photochemical catalyst does not improve substantially relative to sugarcane top photochemical catalyst.
A kind of embodiment 2: preparation method of ligand/plant photochemical catalyst
Terephthalic acid (TPA)/reed Leaves photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (reed Leaves)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
1) first sugarcane top is cleaned, is cut into strip；
2) sugarcane top cut into inch strips is placed in Muffle furnace in temperature is 280 DEG C of roasting 6h, then is 500 DEG C in temperature and roasts
12h；
3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 107mg plant photochemical catalyst, 65.8mg ligand (terephthalic acid (TPA) H2BDC it is molten) to be added to 50mL
It is 110 DEG C, reacts 3d or more under stirring condition in agent (N,N-dimethylformamide) and in temperature；It is cooled to room temperature, is centrifuged, washes
It washs purifying, be drying to obtain ligand/plant photochemical catalyst；Wherein plant photochemical catalyst and the mass ratio of ligand (terephthalic acid (TPA)) are
107:65.8；
Terephthalic acid (TPA)/maize leaves photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (maize leaves)；Wherein plant photochemical catalyst is made in plant leaf blade
The specific steps are
1) first sugarcane top is cleaned, is cut into strip；
2) sugarcane top cut into inch strips is placed in Muffle furnace in temperature is 260 DEG C of roasting 6h, then is 450 DEG C in temperature and roasts
12h；
3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 107mg plant photochemical catalyst, 65.8mg ligand (terephthalic acid (TPA) H2BDC it is molten) to be added to 50mL
It is 110 DEG C, reacts 3d or more under stirring condition in agent (N,N-dimethylformamide) and in temperature；It is cooled to room temperature, is centrifuged, washes
It washs purifying, be drying to obtain ligand/plant photochemical catalyst；Wherein plant photochemical catalyst and the mass ratio of ligand (terephthalic acid (TPA)) are
107:65.8；
Terephthalic acid (TPA)/maple leaf photochemical catalyst preparation method:
(1) plant photochemical catalyst is made in plant leaf blade (maple leaf)；Wherein the tool of plant photochemical catalyst is made in plant leaf blade
Body step is
1) first sugarcane top is cleaned, is cut into strip；
2) sugarcane top cut into inch strips is placed in Muffle furnace in temperature is 280 DEG C of roasting 6h, then is 480 DEG C in temperature and roasts
10h；
3) natural cooling cools down, and is ground into powdered plant photochemical catalyst later；
(2) by step (1) 107mg plant photochemical catalyst, 65.8mg ligand (terephthalic acid (TPA) H2BDC it is molten) to be added to 50mL
It is 110 DEG C, reacts 3d or more under stirring condition in agent (N,N-dimethylformamide) and in temperature；It is cooled to room temperature, is centrifuged, washes
It washs purifying, be drying to obtain ligand/plant photochemical catalyst；Wherein plant photochemical catalyst and the mass ratio of ligand (terephthalic acid (TPA)) are
107:65.8；
Terephthalic acid (TPA)/reed Leaves photochemical catalyst, terephthalic acid (TPA)/maize leaves photochemical catalyst and terephthalic acid (TPA)/maple leaf
Photochemical catalyst photo catalytic reduction CO2:
(1) the 5-50mg catalyst weighed up is added in photo catalysis reactor, then tri- second of 0.1-3mL is added wherein
The mixed solution of hydramine and 0.1-10mL pure water composition, is constantly stirred later, keeps its evenly dispersed；
(2) appropriate vacuum grease will be coated at ball milling and reactor is fixed on reaction unit, opens condensation cycle later
Pump, and it is 5 DEG C that temperature, which is arranged, covers quartz cover after system temperature is stablized；
(3) vacuum pump is opened, the knob on reaction unit is slowly screwed to reactor pressure maintaining from pipeline circulation, system is kept
Evacuated state is constant, this when, system started to vacuumize reactor, and reactor sample introduction is constantly turned in vacuum
Valve prevents dead volume from occurring.Evacuated state keeps 30min or more；
(4) carrier gas and gas-chromatography are opened, is set according to operating condition, is raised to finger to column temperature, detector, reburner
After determining temperature, manual ignition is carried out to chromatography, " water mist " to appear opens acquisition software afterwards, starts to acquire baseline；
(5) knob on reaction unit is screwed at system circulation after vacuumizing, system starts the cycle at this time, at this time
By CO2Gas cylinder is connected at reactor sampling valve, uses CO2Reaction environment is replaced, number is 5-6 times；
(6) reaction unit is got into system circulation by vacuumizing after, keeps 5min；
(7) CO of 8mL is squeezed into reaction unit with syringe2Gas, observing response device pressure registration, confirms later
Gas opens jump pump after being successfully entered reaction system, keeps 1h；
(8) light source is opened, frame reacts 4h, take a sample every 1h right above reactor；
The terephthalic acid (TPA) of embodiment 1/sugarcane top photochemical catalyst, terephthalic acid (TPA)/reed Leaves photochemical catalyst, terephthaldehyde
Acid/maize leaves photochemical catalyst and terephthalic acid (TPA)/maple leaf photochemical catalyst photo catalytic reduction CO2When CO yield figure see Fig. 2, from figure
2 it is found that terephthalic acid (TPA)/reed Leaves photochemical catalyst, terephthalic acid (TPA)/maize leaves photochemical catalyst and terephthalic acid (TPA)/maple leaf light
The photocatalytic activity of catalyst is higher, terephthalic acid (TPA)/sugarcane top photochemical catalyst catalytic activity highest of embodiment 1, right
Phthalic acid/reed Leaves photochemical catalyst CO yield has reached 9.78 μm of olg-1·h-1, terephthalic acid (TPA)/reed Leaves light urges
The catalytic activity of agent is slightly below terephthalic acid (TPA)/sugarcane top photochemical catalyst catalytic activity.
Claims (8)
1. a kind of ligand/plant photochemical catalyst preparation method, which is characterized in that specific step is as follows:
(1) plant photochemical catalyst is made in plant leaf blade；
(2) by step (1) plant photochemical catalyst, ligand be added in solvent and temperature be 25~180 DEG C, under stirring condition it is anti-
Answer 3d or more；It is cooled to room temperature, is centrifuged, purifies, being drying to obtain ligand/plant photochemical catalyst.
2. ligand/plant photochemical catalyst preparation method according to claim 1, it is characterised in that: leaves of plants in step (1)
The specific steps of plant photochemical catalyst are made in piece are as follows:
1) first plant leaf blade is cleaned, is cut into strip；
2) plant leaf blade cut into inch strips is placed in temperature is 150~280 DEG C of 2~10h of roasting, then being placed in temperature is 300~500 DEG C
Roasting 10~for 24 hours, cool to room temperature with the furnace, then be ground into powder up to plant photochemical catalyst.
3. ligand/plant photochemical catalyst preparation method according to claim 1, it is characterised in that: leaves of plants in step (1)
Piece is Leaf-Blade of Poaceae or Aceraceae plant leaf blade.
4. ligand/plant photochemical catalyst preparation method according to claim 3, it is characterised in that: Leaf-Blade of Poaceae
For Sugarcane Leaves, Reed Leaf or maize leaf, Aceraceae plant leaf blade is maple leaves.
5. ligand/plant photochemical catalyst preparation method according to claim 1, it is characterised in that: step (2) ligand is pair
Phthalic acid or trimesic acid.
6. ligand/plant photochemical catalyst preparation method according to claim 1, it is characterised in that: plant photochemical catalyst with
The mass ratio of ligand is (20~1): 1.
7. ligand/plant photochemical catalyst preparation method according to claim 1, it is characterised in that: step (2) solvent is N,
Dinethylformamide, methanol, deionized water it is one or more.
8. ligand/plant photochemical catalyst prepared by any one of claim 1~7 ligand/plant photochemical catalyst preparation method
In photo catalytic reduction CO2In application.
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