CN103301856A - Application of nano noble metal/semiconductor composite photocatalyst to halogenation reaction of organic matters - Google Patents
Application of nano noble metal/semiconductor composite photocatalyst to halogenation reaction of organic matters Download PDFInfo
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Abstract
The invention relates to an application of a nano noble metal/semiconductor surface plasma composite material as a photocatalyst to a halogenation reaction process of organic matters. By virtue of the photocatalyst, halogen ions X- provided by inorganic halogen acid salt M+X- dissolved in a water phase can be taken as a halogenation agent in the halogenation reaction process of the organic matters, the halogen ions X- are directly converted into halogen atom free radicals under the irradiation of visible light or sunlight, and halogen substitution or addition reaction of the organic matters is initiated. According to the application, a novel, environment-friendly, high-selectivity and low-energy way for synthesizing organic halides is created.
Description
Technical field
The present invention relates to nano-noble metal/semiconductor surface plasma composite as application, the especially application in organic halogenation of photochemical catalyst.
Background technology
The utilization of solar energy is extensively paid attention to, as photovoltaic energy and natural photosynthesis.Semiconductor by solar energy make water decomposition produce hydrogen, the photosynthesis conversion solar can be biomass energy, initiated oxidation reduction reaction etc., all these just " green living " of sustainable development advocate.Photocatalysis is described as vitochemical new way of 21 century, TiO
2, ZnO, AgCl and composite load type inorganic semiconductor thereof be exactly photochemical catalyst typical case representative.Based on the semiconductor light-catalyst of composite Nano precious metals ag, Au, Pt, Pd etc., as Ag/AgX (X=Cl, Br, I), Ag/ZnO, Ag/AgCl/TiO
2, Ag/Ag
3PO
4, Au/TiO
2, Au/ZnO, Pt/TiO2, Cu
2O/TiO
2Deng, because the nano metal that is compounded in semiconductor material surface has the surface plasma body resonant vibration effect, thereby make it to visible light strong absorption be arranged, have good photo-catalysis capability, and obtained success at aspects such as oxidation, light degradation organic matter, photodissociation aquatic products hydrogen.
Yet the related compound material is applied in the organic photocatalysis halogenation process, does not appear in the newspapers as yet.
Halogenation is one of key reaction common during organic synthesis and fine chemicals are produced, and halogenating agent and the halogenation of studying novel, environmental protection, high selectivity, low energy consumption are the targets that chemical is sought always.Cl
2, Br
2, I
2Deng being the most frequently used halogenating agent, not only production process is tediously long, seriously polluted for elemental halogen, energy consumption is high, and very dangerous; From application point of view see its reaction selectivity is relatively poor, corrosivity is strong, seriously polluted.Therefore, develop a kind of alkali halide (halogen acid salt) that directly utilizes and realize relevant halogenation method for halogenating agent substitutes elemental halogen, its economic benefit, safe meaning, the environment protection significance that can bring be self-evident, yet correlative study and embodiment still belong to blank, and its difficulty has some idea of.
Summary of the invention
The present invention is applied to organic halogenation process with nano-noble metal/semiconductor surface plasma composite, making organic halogenation can be the halogen source with the inorganic halides (halogen acid salt) that is dissolved in the inorganic phase (as water), under visible light or irradiation of sunlight, directly make the halogen ion change the halogen free radical into, and cause halogenation.
Wherein, described nano-noble metal/semiconductor surface plasma composite is selected from following group: Nano Silver/silver chlorate, Nano Silver/silver chlorate/bismuth oxygen chlorine, Nano Silver/chlorination silver/titanium dioxide, Nano Silver/silver chlorate/wolframic acid silver, nm of gold/silver chlorate, nm of gold/titanium dioxide, nanometer platinum/silver chlorate, nanometer platinum/titanium dioxide, nano cuprous oxide/silver chlorate and nano cuprous oxide/titanium dioxide and aforementioned every any combination; Wherein be preferably, described nano-noble metal/semiconductor surface plasma composite is Nano Silver/silver chlorate, nm of gold/silver chlorate, nm of gold/titanium dioxide, nanometer platinum/silver chlorate, nanometer platinum/titanium dioxide, nanometer palladium/silver chlorate, nano cuprous oxide/silver chlorate.
Wherein, nano-noble metal/semiconductor surface plasma composite is applied in two key halogen addition reaction of the halogenating reaction of halogenating reaction, alkylaromatic hydrocarbon of alkane and alkene.
Wherein, above-mentioned Nano Silver/silver chlorate composite is that following steps are obtained:
Step (1): the silver chlorate micron cube of preparation graded structure: be dissolved in silver nitrate and potassium chloride or sodium chloride in the water respectively, mixing the back fully stirs, transfer in the enclosed autoclave at last, after placing 140-200 ℃ to react the scheduled time down, after being cooled to room temperature, with product collection, washing, vacuum drying, obtain the silver chlorate micron cube of the graded structure of high-crystallinity;
Step (2): preparation Nano Silver/silver chlorate composite: the immersion of silver chlorate micron cube material is contained the aqueous solution of silver nitrate and adds reducing agent, the 300W xenon lamp according under or shine under the sunshine, make wherein silver chlorate and silver nitrate partial reduction generate simple substance silver, namely obtain Nano Silver/silver chlorate composite, silver-colored load capacity reaches 3.0～12.8mol%.
Wherein, the reducing agent used of described step (2) is formalin, methyl orange, formic acid, formates or glucose.
Nano Silver/silver chlorate composite that said method is prepared, the high capacity amount of silver reaches 12.8%, for the conversion ratio of the direct chlorination that improves the catalysis chlorion is laid a good foundation.
Wherein, nm of gold/silver chlorate, the preparation method of nm of gold/titanium dioxide comprises:
Described nm of gold/silver chlorate, nm of gold/titanium dioxide surface plasma composite are that following steps are obtained:
Step (1): with the ethylene glycol of 10-80ml and AgCl powder or the TiO of 1.4-34.9mmol
2(Degussa P25) joins in the reactor powder, and supersonic oscillations 20min or stirring 30min with 100W make AgCl powder or TiO
2Powder is scattered in the ethylene glycol uniformly;
Step (2): reactor is heated to 120-200 ℃ in oil bath, be full of nitrogen in reactor, adding Vc concentration simultaneously is that the ethylene glycol solution 3-10ml of 3mmol/L and the concentration of PVP are ethylene glycol solution 15-50ml and the 30mg lauryl amine of 0.18mol/L;
Step (3): continue to stir the HAuCl that adds 29.4mmol again
4Solution 0.5-5ml directly transfers to reactor in the ice-water bath behind the reaction 2h-6h, after the cooling, in 60 ℃ of baking oven baking 4h, namely obtains photochemical catalyst Au/AgCl or Au/TiO after centrifugal and deionized water washing
2Composite, wherein Jin load capacity reaches 2.5-6.6mol%.
The present invention adopts the collaborative reducing agent of vitamin C (Vc) and lauryl amine in the preparation of the composite catalyst (as nm of gold/silver chlorate, nm of gold/titanium dioxide) of high capacity nm of gold, make the load capacity of nm of gold reach 6.6mol%.
Degussa P25 type titanium dioxide is the titanium dioxide that German Degussa degussa company produces with the vapor phase method production technology, because its basic granules particle diameter has only 20nm, this a kind of titanium dioxide is used to as the UV resistant agent in photochemical catalyst, catalyst, catalyst carrier, cosmetics and the weaving, the industries such as heat stabilizer of silicon rubber almost without any the pigment feature.
Described nanometer palladium/silver chlorate composite is that following steps are obtained:
Step (1): get a certain amount of AgCl powder and chloroplatinic acid H
2PdCl
6Join in the distilled water, and vigorous stirring, make even dispersion obtain mixed liquor;
Step (2): to 6.8-7.0, in this mixed liquor, drip NaBH with KOH solution regulating step (1) gained pH of mixed value
3(CN) ethanolic solution is constant to the solution color and luster;
Step (3): vigorous stirring under the room temperature, centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, 110 ℃ times dryings, obtain visible-light photocatalyst Pd/AgCl at last.
Wherein, the consumption of each reactant can the materially affect product in above-mentioned preparation method's step acquisition and physicochemical properties only influence product yield and reaction speed, select the just comparatively suitable magnitude relation of using of above-mentioned concrete consumption proportion relation.
Zhi Bei nano-noble metal/semiconductor surface plasma composite in the above described manner, wherein the load capacity of nano-noble metal reaches 2.5-6.6mol%, therefore has high load capacity, in light-catalyzed reaction, has higher catalytic efficiency.
Wherein, nanometer platinum/silver chlorate that the present invention uses, the preparation method of nanometer platinum/titanium dioxide comprises:
Step (1): the AgCl powder or the TiO that get 1.4-34.9mmol
2The chloroplatinic acid of powder (Degussa P25) and 0.17-0.51mmol successively joins in the reactor that distilled water is housed, and vigorous stirring makes it evenly to be dispersed into suspension;
Step (2): splash into the KOH solution of 0.1mol/L in the above-mentioned reactor, the pH value that detects suspension is adjusted to 6.8-7.0, the NaBH of dropping 10mmol/L
3(CN) ethanolic solution is constant to the solution color and luster;
Step (3): vigorous stirring under the room temperature, products obtained therefrom are carried out centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, last 110 ℃ times dryings obtain visible-light photocatalyst Pt/AgCl or Pt/TiO
2
Wherein, the consumption of each reactant can the materially affect product in above-mentioned preparation method's step acquisition and physicochemical properties only influence product yield and reaction speed, select the just comparatively suitable magnitude relation of using of above-mentioned concrete consumption proportion relation.
Among the present invention, nanometer platinum/silver chlorate, the preparation method of nanometer platinum/titanium dioxide utilizes NaBH
3(CN) selective reduction chloroplatinic acid has been realized the selective load of nanometer platinum in the presence of silver salt.
The catalytic mechanism of photochemical catalyst of the present invention is to be dissolved in inorganic inorganic hydrogen halate M in mutually
+X
-Be the halogen source, with nano-noble metal/semiconductor surface plasma composite as photochemical catalyst, utilize the surface plasma bulk effect of photocatalyst compound material, high efficiency absorption and utilize sunshine or the energy of other visible lights, the semiconductor space of composite is shifted an electronics of halogen ion and is made it to be converted into the halogen atom free radical, thereby causes free fundamental mode halogenation.The present invention is applied in nano-noble metal/semiconductor composite in the organic halogenation, organic halo or halogen addition reaction can be carried out at normal temperatures, and utilize the energy of the sunshine of nature, so this is the organic matter halogenation method of a kind of novel, environmental protection, high selectivity, low energy consumption.
Description of drawings
Fig. 1 shows the SEM figure of Nano Silver of the present invention/high-crystallinity silver chlorate catalysis material.
Fig. 2 shows the XRD figure of Nano Silver/high-crystallinity silver chlorate catalysis material.
Fig. 3 shows content of nanometer silver in the Ag/AgCl photochemical catalyst and the graph of a relation of toluene optical chlorinating reaction conversion ratio.
The specific embodiment
Following mask body is introduced preparation method and application's example of nano-noble metal/semiconductor surface plasma composite:
Embodiment 1: the preparation of Nano Silver/silver chlorate:
0.167g silver nitrate and 5.2g potassium chloride are dissolved in respectively in 10ml and the 70ml deionized water, mix the back and stir 30min, be transferred at last in the airtight 100ml autoclave.Place 165 ℃ of down reactions 4 hours, to be cooled to room temperature, product is collected, washing, vacuum drying obtains the silver chlorate micron cube of the graded structure of high-crystallinity.
Silver chlorate micron cube powder is joined in the aqueous solution that has dissolved 0.167g silver nitrate and 0.02-0.2mol formalin, shine 30min with the 300W xenon lamp, part silver chlorate and silver nitrate reduction generate silver-colored simple substance, finally obtain the heterogeneous visible-light photocatalysis material of high capacity Nano Silver/silver chlorate.The load capacity of silver reaches 12.8mol%.
Embodiment 2: the preparation of Nano Silver/silver chlorate:
0.255g silver nitrate and 5.2g potassium chloride are dissolved in respectively in 10ml and the 70ml deionized water, mix the back and stir 30min, be transferred at last in the airtight 100ml autoclave.Place 175 ℃ of down reactions 5.5 hours, to be cooled to room temperature, product is collected, washing, vacuum drying obtains the silver chlorate micron cube of the graded structure of high-crystallinity.
Silver chlorate micron cube powder is joined in the aqueous solution that has dissolved 0.255g silver nitrate and 0.02-0.2mol sodium formate, shine 35min with the 300W xenon lamp, part silver chlorate and silver nitrate reduction generate silver-colored simple substance, finally obtain the Nano Silver/silver/silver chloride visible light photocatalysis material of high capacity, the nanometer Ag load capacity is 4.6-8.7mol%.
SEM figure and the XRD figure (seeing shown in Fig. 1-2) of the high capacity Nano Silver of method for preparing/high-crystallinity silver chlorate catalysis material, the content of Ag is 8.7mol%, the content of AgCl is 91.3%.Nano-Ag particles is embedded on the silver chlorate micron cube, has formed stable heterogeneous semiconductor composite photocatalyst material.
Embodiment 3: the preparation of Nano Silver/silver chlorate:
0.167g silver nitrate and 5.2g potassium chloride are dissolved in respectively in 10ml and the 70ml deionized water, mix the back and stir 30min, place 165 ℃ to react 4 hours down, to be cooled to room temperature, product is collected washing, vacuum drying obtains the silver chlorate micron cube of the graded structure of high-crystallinity.
Silver chlorate micron cube powder is joined in the aqueous solution that has dissolved 0.167g silver nitrate and formic acid, shine 30min with the 300W xenon lamp, the silver nitrate reduction generates silver-colored simple substance, finally obtains the heterogeneous visible-light photocatalysis material of high capacity Nano Silver/silver chlorate, and the load capacity of silver reaches 3.0mol%.
Embodiment 4: the preparation of nanometer platinum/silver chlorate:
The homemade AgCl powder of 1g and 0.05g chloroplatinic acid H
2PtCl
6After join in 75 milliliters the distilled water and vigorous stirring 10 minutes.Regulate the pH of mixed value to 6.8-7.0 with the KOH solution of 0.1M, drip 10mM NaBH
3(CN) ethanolic solution is constant to the solution color and luster.Vigorous stirring is 1 hour under the room temperature, centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, last 110 ℃ times dry 12h obtain visible-light photocatalyst Pt/AgCl.
Embodiment 5: the preparation of nanometer platinum/titanium dioxide:
The commercially available TiO of 1g
2Powder (Degussa P25) and 0.05g chloroplatinic acid H
2PtCl
6After join in 75 milliliters the distilled water and vigorous stirring 10 minutes.Regulate the pH of mixed value to 6.8-7.0 with the KOH solution of 0.1M, drip 10mM NaBH
3(CN) ethanolic solution is constant to the solution color and luster.Vigorous stirring is 3 hours under the room temperature, centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, last 110 ℃ times dry 12h obtain visible-light photocatalyst Pt/TiO
2
Embodiment 6: the preparation of nm of gold/silver chlorate:
Diglycol and the homemade AgCl powder of 0.5g of 80ml are joined round-bottomed flask, be 100w ultrasonic echography 20min with power, vigorous stirring 30min makes it to be uniformly dispersed, in oil bath, be heated to 150 ℃, after in round-bottomed flask, being full of argon gas, add the diglycol solution 3ml of 3mmol/L Vc and the diglycol solution 15ml of 0.18mol/L PVP simultaneously, continue to stir the HAuCl4 solution 0.5ml that adds 10mg/ml again, directly transfer to round-bottomed flask in the ice-water bath behind the reaction 2h, after the cooling, after centrifugal and deionized water washing, in 60 ℃ of baking oven baking 4h, namely get described visible-light photocatalyst Au/AgCl.
Embodiment 7: the preparation of nm of gold/titanium dioxide:
Ethylene glycol and the commercially available TiO of 0.5g with 80ml
2(Degussa P25) joins round-bottomed flask to powder, be the ultrasonic echography 20min of 100w with power, and vigorous stirring 30min makes it to be uniformly dispersed.Under the argon shield condition, in 150 ℃ of oil baths, heat, add the ethylene glycol solution 3ml of 3mmol/L Vc and the ethylene glycol solution 15ml of 0.18mol/L PVP.When stirring, add the HAuCl of 10mg/ml
4Solution 0.5ml directly transfers to round-bottomed flask in the ice-water bath behind the reaction 2h and cools off, and dries by the fire 4h through centrifugal and deionized water washing back in 60 ℃ of baking ovens, namely gets described visible-light photocatalyst Au/TiO
2
Embodiment 8: the preparation of nanometer palladium/silver chlorate:
1g AgCl powder and 0.05g chloroplatinic acid H
2PdCl
6After join in 75 milliliters the distilled water and vigorous stirring 10 minutes.Regulate the pH of mixed value to 6.8-7.0 with the KOH solution of 0.1M, drip 10mM NaBH
3(CN) ethanolic solution is constant to the solution color and luster.Vigorous stirring is 1 hour under the room temperature, centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, last 110 ℃ times dry 12h obtain visible-light photocatalyst Pd/AgCl.
Embodiment 9: the preparation of nano cuprous oxide/silver chlorate:
The hydrated copper acetate of 1.4g is dissolved in 100 milliliters of ethanol, adds the homemade AgCl powder of 1g then, ultrasonicly be separated into uniform suspension.In 60 ℃ of water-bath heating, and respectively with speed adding 100 milliliters of formalins (0.2mol/L) of 80ml/min and 120 milliliters the NaOH solution of 0.3M, centrifugation precipitates, and cleans 3 times at absolute ethyl alcohol and distilled water, dry 12h in a vacuum namely gets Cu/AgCl at last.
Embodiment 10: the preparation of nano cuprous oxide/titanium dioxide:
The hydrated copper acetate of 1.4g is dissolved in 100 milliliters of ethanol, adds commercially available 1gTiO then
2Powder (Degussa P25) ultrasonicly is separated into uniform suspension.In 60 ℃ of water-bath heating, and respectively with speed adding 100 milliliters of formalins (0.2mol/L) of 80ml/min and 120 milliliters the NaOH solution of 0.3M, centrifugation precipitates, and cleans 3 times at absolute ethyl alcohol and distilled water, dry 12h in a vacuum namely gets Cu/TiO at last
2
More than enumerated the preparation method of part nano-noble metal/semiconductor surface plasma composite.Below be as photochemical catalyst about nano-noble metal/semiconductor surface plasma composite, with inorganic halide (halogen ion) be dissolved in inorganic mutually in as halogenating agent, be applied in the embodiment in the organic halogenation, wherein comprise the embodiment that two key halogen addition of the selective halo, alkene or the alkene derivatives that are applied in alkane, the selective α of alkyl aromatic-hydrogen halogen replace respectively.
Embodiment 11: Nano Silver/silver chlorate composite material photocatalyst is applied to the halogenation process of isopentane:
(1) 7g potassium chloride, 2.5ml hydrochloric acid (mass fraction 31%) are added in the 50ml deionized water, obtain the aqueous solution of potassium chloride, in order to chlorion to be provided;
(2) potassium chloride solution is put into Photoreactor, add 0.3g Nano Silver/silver chlorate surface plasma composite material photocatalyst (load capacity of Nano Silver reaches 8.6mol%), 0.05g tetrabutylammonium chloride (as phase transfer catalyst, further improving reaction efficiency) and 25ml isopentane (reaction substrate is alkanes) in the phototropic reaction device;
(3) under agitation, use the irradiation of sunshine or 300W xenon lamp, stirring reaction 6h under the normal temperature stops to stir;
(4) filtering recovering catalyst is isolated water and is reclaimed usefulness again, gets the organic phase sample and analyzes with GS, conversion ratio 32%.The organic phase drying, isopentane gas-chromatography conversion ratio 28%.Atmospheric distillation is collected the cut of 83-85 ° of C, 2-methyl-2 chlorobutane, yield 92%.
Embodiment 12: nanometer platinum/silver chlorate composite material photocatalyst is applied to the halogenation process of isopentane:
With the Nano Silver/silver chlorate among nanometer platinum/silver chlorate replacement embodiment 11, other conditions are identical.Isopentane gas phase conversion rate 29%, the yield 91% of 2-methyl-2 chlorobutane.
Embodiment 13: nm of gold/silver chlorate composite material photocatalyst is applied to the halogenation process of isopentane:
Replace Nano Silver/silver chlorate among the embodiment 11 with nm of gold/silver chlorate, other conditions are identical.Isopentane gas phase conversion rate 30%, the yield 92% of 2-methyl-2 chlorobutane.
Embodiment 14: nano cuprous oxide/silver chlorate composite material photocatalyst is applied to the halogenation process of isopentane
With the Nano Silver/silver chlorate among nano cuprous oxide/silver chlorate replacement embodiment 11, other conditions are identical.Isopentane gas phase conversion rate 12%, the yield 67% of 2-methyl-2 chlorobutane.
Embodiment 15: nm of gold/composite titania material photocatalyst applications is in the halogenation process of isopentane
With the Nano Silver/silver chlorate among nm of gold/titanium dioxide replacement embodiment 11, other conditions are identical.Isopentane gas phase conversion rate 16%, the yield 71% of 2-methyl-2 chlorobutane.
Embodiment 16: Nano Silver/composite titania material photocatalyst applications is in the halogenation process of isopentane
With the Nano Silver/silver chlorate among the nanometer silver/titanium dioxide replacement embodiment 11, other conditions are identical.Isopentane gas phase conversion rate 18%, the yield 74% of 2-methyl-2 chlorobutane.
Embodiment 11-16 adopts nano-noble metal/semiconductor surface plasma composite as photochemical catalyst, when participating in the halogenating reaction of alkane, the aqueous solution that can the inorganic hydrogen halate as halogenating agent (as potassium chloride, sodium-chloride water solution), and do not need to provide halogen simple substance, the halogen that can carry out alkane under visible light radiation conditions such as sunshine expeditiously replaces, and have the selective of preferred alkane substitute uncle position H, therefore, with nano-noble metal/semiconductor surface plasma composite as photochemical catalyst, can make the halogenating reaction product of alkane more single, the purity height, it is easier to separate.
Embodiment 17: Nano Silver/silver chlorate composite material photocatalyst is applied in the selective addition process of the two keys of styrene:
(1) 7g sodium chloride, 2.5ml hydrochloric acid (mass fraction 31%) are added in the 50ml deionized water, obtain the aqueous solution of sodium chloride, so that chlorion to be provided;
(2) aqueous solution of sodium chloride is put into Photoreactor, adds 0.45g Nano Silver/silver chlorate surface plasma composite material photocatalyst (load capacity of Nano Silver reaches 7.2mol%), 0.05g tetrabutylammonium chloride (as phase transfer catalyst) and 15ml styrene (reaction substrate is alkene) again;
(3) open the irradiation of 300W xenon lamp, stirring reaction 6h under the normal temperature stops to stir;
(4) filtering recovering catalyst is isolated organic phase, and water reclaims and uses; Sampling is analyzed with GS, conversion ratio 32%.Organic phase drying, decompression distillation get 1,2-, two chloro-1-diphenylphosphino ethanes, yield 78%.GC-MS: molecular formula: C
8H
8Cl
2Calculated value: 174.00 and 175.99; Measured value (M+1): 175.12 and 177.05.
Embodiment 18: nanometer platinum/silver chlorate composite material photocatalyst is applied in the selective addition process of the two keys of styrene:
Replace Nano Silver/silver chlorate among the embodiment 17 with nanometer platinum/silver chlorate, other conditions are identical.Styrene inversion of phases rate 38%, 1,2-two chloro-1-diphenylphosphino ethane yields 88%.
Embodiment 19: nm of gold/silver chlorate composite material photocatalyst is applied to the selective addition process of the two keys of styrene:
Replace receiving Nano Silver/silver chlorate among the embodiment 17 with nm of gold/silver chlorate, other conditions are identical.Styrene inversion of phases rate 36%, 1,2-two chloro-1-diphenylphosphino ethane yields are 85%.
Embodiment 20: nano cuprous oxide/silver chlorate composite material photocatalyst is applied to the selective addition process of the two keys of styrene
Replace Nano Silver/silver chlorate among the embodiment 17 with nano cuprous oxide/silver chlorate, other conditions are identical.Styrene inversion of phases rate 24%, 1,2-two chloro-1-diphenylphosphino ethane yields are 73%.
Embodiment 21: nm of gold/composite titania material photocatalyst applications is in the selective addition process of cinnamic pair of key
Replace Nano Silver/silver chlorate among the embodiment 17 with nm of gold/titanium dioxide, other conditions are identical.Styrene inversion of phases rate 28%, 1,2-two chloro-1-diphenylphosphino ethane yields are 78%.
Embodiment 22: Nano Silver/composite titania material photocatalyst applications is in the selective addition process of the two keys of styrene
Replace Nano Silver/silver chlorate among the embodiment 17 with the nanometer silver/titanium dioxide, other conditions are identical.Styrene inversion of phases rate 23%, 1,2-two chloro-1-diphenylphosphino ethane yields are 72%.
Embodiment 17-22, adopt nano-noble metal/semiconductor surface plasma composite as photochemical catalyst, when participating in the two key addition reaction of alkene or alkene derivatives, the aqueous solution that can halogen acid salt is as halogenating agent (sodium-chloride water solution), and do not need to provide halogen simple substance, can under visible light radiation conditions such as sunshine, carry out the selective addition of the two keys of alkene expeditiously, make halogen addition reaction product more single, the purity height, separate easier.
Embodiment 23: Nano Silver/silver chlorate photoreactivation material light catalysis agent is applied to alkylaromatic hydrocarbon α-hydrogen halogenating reaction process:
(1) add 50ml deionized water, 7g sodium chloride and 2.5ml hydrochloric acid (31%) respectively in photo catalysis reactor, stirring makes sodium chloride soluble in water, so that chlorion to be provided;
(2) add 0.3g Nano Silver/silver chlorate photochemical catalyst (the Nano Silver load capacity reaches 8.6mol%) and 0.05g tetrabutylammonium chloride again as phase transfer catalyst, add 15ml toluene (reaction substrate) at last, strong agitation;
(3) open 300W xenon lamp irradiation or merely with solar light irradiation after the stirring and dissolving again, react 5h under the normal temperature;
(4) filtering recovering catalyst is isolated organic phase, and water reclaims and uses; Sampling is analyzed with GS, and conversion ratio 42% does not detect many chloro-products.The cut of 176.5-179 ° of C is collected in rectifying, gets benzyl chloride, yield 95%.
See also shown in Figure 3ly, show content of nanometer silver in the Ag/AgCl photochemical catalyst and the graph of a relation of toluene optical chlorinating reaction conversion ratio.Content of nanometer silver in the basic and Ag/AgCl photochemical catalyst of expression toluene optical chlorinating reaction conversion ratio slightly is a proportional relationship.
Embodiment 24: replace potassium chloride and concentrated hydrochloric acid with KBr and concentrated hydrobromic acid, other conditions are identical with 23, and the reaction substrate alkylaromatic hydrocarbon is chosen as toluene, conversion ratio 36%.The cut of 197-198.5 ° of C, benzyl bromide a-bromotoluene yield 89% are collected in rectifying.
Embodiment 25: the alkylaromatic hydrocarbon of reaction substrate is chosen as the 2-methyl naphthalene, and other conditions are identical with 23, the conversion ratio 32% of methyl naphthalene.Separate and adopt rectification under vacuum, collect 133-135.5 ° of C/20mmHg cut, yield 78%
Embodiment 26: the alkylaromatic hydrocarbon of reaction substrate is the 2-methylthiophene, and other conditions are identical with 23, conversion ratio 28%.Separate and adopt rectification under vacuum, collect 78-81.5 ° of C/18mmHg cut, yield 83%.
Embodiment 27: nanometer platinum/silver chlorate composite material photocatalyst is applied to the selective substitution reaction process of alkylaromatic hydrocarbon α-H:
Replace Nano Silver/silver chlorate among the embodiment 23 with nanometer platinum/silver chlorate, with the irradiation of 300W xenon lamp, other conditions are identical.Toluene inversion of phases rate 33%, benzyl chloride yield 90%.
Embodiment 28: replace Nano Silver/silver chlorate among the embodiment 23 with nanometer platinum/silver chlorate, adopt solar radiation, other conditions are identical.Toluene inversion of phases rate 30%, benzyl chloride yield 91%.
Embodiment 29: replace Nano Silver/silver chlorate among the embodiment 23 with nanometer platinum/silver chlorate, replace potassium chloride and concentrated hydrochloric acid with KBr and concentrated hydrobromic acid, other conditions are identical.Toluene inversion of phases rate 35%, benzyl bromide a-bromotoluene yield 89%.
Embodiment 30: change the reaction substrate of the step (2) of embodiment 23 into ethylbenzene, other reaction conditions are all identical, then change the change rate 28% of ethylbenzene, alpha-chloro ethylbenzene yield 82%.
Embodiment 31: in embodiment 23, replace potassium chloride and concentrated hydrochloric acid with KBr and concentrated hydrobromic acid, reaction substrate changes ethylbenzene into, other conditions are identical, and then conversion of ethylbenzene 32%, rectification under vacuum, collect 93-94.5 ° of C/16mmHg cut, the yield 77% of the alpha-brominated ethylbenzene of product.
Embodiment 32: with the photochemical catalyst of Nano Silver/silver chlorate among nm of gold/silver chlorate replacement embodiment 23, other conditions are identical.Toluene inversion of phases rate is 38%, benzyl chloride yield 96%.
Embodiment 33: with the photochemical catalyst of Nano Silver/silver chlorate among nm of gold/silver chlorate replacement embodiment 23, reaction substrate replaces with ethylbenzene by toluene, and other conditions are identical.Conversion of ethylbenzene 29%, product alpha-chloro ethylbenzene yield be 82%.
Embodiment 34: nano cuprous oxide/silver chlorate composite material photocatalyst is applied to the selective substitution reaction process of alkylbenzene α-H:
Replace Nano Silver/silver chlorate among the embodiment 23 with nano cuprous oxide/silver chlorate, adopt the irradiation of 300W xenon lamp, other conditions are identical.Toluene inversion of phases rate 29%, benzyl chloride yield 87%.
Embodiment 35: replace Nano Silver/silver chlorate among the embodiment 23 with nano cuprous oxide/silver chlorate, adopt solar radiation, other conditions are identical.Toluene inversion of phases rate 26%, benzyl chloride yield 88%.
Embodiment 36: with the Nano Silver/silver chlorate among nano cuprous oxide/silver chlorate replacement embodiment 23, with potassium chloride and concentrated hydrochloric acid among KBr and the concentrated hydrobromic acid replacement embodiment 23, other conditions are identical.Toluene inversion of phases rate 32%, benzyl bromide a-bromotoluene yield 87%.
Embodiment 37: nm of gold/composite titania material photocatalyst applications is in the selective substitution reaction process of alkylbenzene α-H:
Replace Nano Silver/silver chlorate among the embodiment 23 with nm of gold/titanium dioxide, other conditions are identical.Toluene conversion 24%, benzyl chloride yield 80%.
Embodiment 38: Nano Silver/composite titania material photocatalyst applications is in the selective substitution reaction process of toluene α-H: replace Nano Silver/silver chlorate among the embodiment 23 with the nanometer silver/titanium dioxide, other conditions are identical.Toluene conversion 23%, benzyl chloride yield 79%.
Embodiment 39: nanometer platinum/composite titania material photocatalyst applications is in the selective substitution reaction process of alkylbenzene α-H: replace Nano Silver/silver chlorate among the embodiment 23 with nanometer platinum/titanium dioxide, other conditions are identical.Toluene conversion 27%, benzyl chloride yield 82%.
By embodiment 23-39 as can be known, when the methylarenes of substrate or ethylaromatics, adopt nano-noble metal/semiconductor surface plasma composite as photochemical catalyst, the aqueous solution that can the inorganic hydrogen halate is as halogenating agent (aqueous solution of sodium chloride, potassium chloride etc.), and do not need to provide halogen simple substance, can under the solar irradiation condition, carry out the selective replacement of alkylaromatic hydrocarbon α-H expeditiously, make the halogenating reaction product more single, the purity height, separate easier.
Claims (13)
1. nano-noble metal/semiconductor surface plasma composite is as photochemical catalyst, the application in the organic halogenation process of photocatalysis.
2. application as claimed in claim 1 is characterized in that: described halogenation process is to be dissolved in inorganic inorganic hydrogen halate M in mutually
+X
-Be the halogen source, under sunlight or visible light radiation, directly make halogen ion X
-Change the halogen free radical into, and cause halogenation.
3. application as claimed in claim 2 is characterized in that: the described inorganic water that is mutually.
4. application as claimed in claim 1, it is characterized in that: described nano-noble metal/semiconductor surface plasma composite is selected from following group: Nano Silver/silver chlorate, Nano Silver/silver chlorate/bismuth oxygen chlorine, Nano Silver/chlorination silver/titanium dioxide, Nano Silver/silver chlorate/wolframic acid silver, nm of gold/silver chlorate, nm of gold/titanium dioxide, nanometer platinum/silver chlorate, nanometer platinum/titanium dioxide, nanometer palladium/silver chlorate, nano cuprous oxide/silver chlorate and nano cuprous oxide/titanium dioxide and aforementioned every any combination.
5. application as claimed in claim 4, it is characterized in that, described nano-noble metal/semiconductor surface plasma composite is Nano Silver/silver chlorate, nm of gold/silver chlorate, nm of gold/titanium dioxide, nanometer palladium/silver chlorate, nanometer platinum/silver chlorate, nanometer platinum/titanium dioxide or nano cuprous oxide/silver chlorate.
6. as claim 1,2 or 4 described application, it is characterized in that: described nano-noble metal/semiconductor surface plasma composite is applied in two key addition halogenations of the halogenating reaction of alkane, the α of alkylaromatic hydrocarbon-hydrogen halogenating reaction and alkene.
7. application as claimed in claim 5 is characterized in that, described Nano Silver/silver chlorate composite is that following steps are obtained:
Step (1): the silver chlorate micron cube of preparation graded structure: be dissolved in silver nitrate and potassium chloride or sodium chloride in the water respectively, mixing the back fully stirs, transfer in the enclosed autoclave at last, after placing 140-200 ℃ to react the scheduled time down, after being cooled to room temperature, with product collection, washing, vacuum drying, obtain the silver chlorate micron cube of the graded structure of high-crystallinity;
Step (2): preparation Nano Silver/silver chlorate composite: the immersion of silver chlorate micron cube material is contained the aqueous solution of silver nitrate and adds reducing agent, the 300W xenon lamp according under or shine under the sunshine, make wherein silver chlorate and silver nitrate partial reduction generate simple substance silver, namely obtain Nano Silver/silver chlorate composite.
8. application as claimed in claim 7 is characterized in that, described reducing agent is formalin, formic acid, formates or glucose.
9. application as claimed in claim 5 is characterized in that, described nm of gold/silver chlorate composite is that following steps are obtained:
Step (1): a certain amount of ethylene glycol and AgCl powder are joined in the reactor, with supersonic oscillations or stirring, make the AgCl powder be scattered in the ethylene glycol uniformly;
Step (2): reactor is heated to 120-200 ℃ in oil bath, in reactor, is full of nitrogen, add the ethylene glycol solution of a certain amount of Vc, the ethylene glycol solution of PVP simultaneously, and a certain amount of lauryl amine;
Step (3): the HAuCl that adds in continuing to stir
4Solution is directly transferred to reactor in the ice-water bath after the reaction, after the cooling, in 60 ℃ of oven for drying, namely obtains photochemical catalyst Au/AgCl composite after centrifugal and deionized water washing.
10. application as claimed in claim 5 is characterized in that, described nm of gold/composite titania material is that following steps are obtained:
Step (1): with a certain amount of ethylene glycol and TiO
2Powder joins in the reactor, with supersonic oscillations or stirring, makes the AgCl powder be scattered in the ethylene glycol uniformly;
Step (2): reactor is heated to 120-200 ℃ in oil bath, in reactor, is full of nitrogen, add the ethylene glycol solution of a certain amount of Vc, the ethylene glycol solution of PVP simultaneously, and a certain amount of lauryl amine;
Step (3): continue to stir the HAuCl that adds again
4Solution is directly transferred to the reactor of this mixed liquor of splendid attire in the ice-water bath after the reaction, after the cooling, in 60 ℃ of oven for drying, namely obtains photochemical catalyst Au/TiO after centrifugal and deionized water washing
2Composite.
11. application as claimed in claim 5 is characterized in that, described nanometer platinum/silver chlorate composite is that following steps are obtained:
Step (1): get a certain amount of AgCl powder and chloroplatinic acid and successively join in the reactor that distilled water is housed, and vigorous stirring makes it evenly to be dispersed into suspension;
Step (2): splash into KOH solution in above-mentioned reactor, the pH value that detects suspension is adjusted to 6.8-7.0, drips NaBH
3(CN) ethanolic solution is constant to the solution color and luster;
Step (3): vigorous stirring under the room temperature, products obtained therefrom are carried out centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, in 110 ℃ times dryings, obtain visible-light photocatalyst Pt/AgCl at last.
12. application as claimed in claim 5 is characterized in that, described nanometer platinum/composite titania material is that following steps are obtained:
Step (1): get a certain amount of TiO2 powder and chloroplatinic acid and successively join in the reactor that distilled water is housed, and vigorous stirring makes it evenly to be dispersed into suspension;
Step (2): splash into KOH solution in above-mentioned reactor, the pH value that detects suspension is adjusted to 6.8-7.0, drips NaBH
3(CN) ethanolic solution is constant to the solution color and luster;
Step (3): vigorous stirring under the room temperature, products obtained therefrom are carried out centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, in 110 ℃ times dryings, obtain visible-light photocatalyst Pt/TiO at last
2
13. application as claimed in claim 5 is characterized in that, described nanometer palladium/silver chlorate composite is that following steps are obtained:
Step (1): get a certain amount of AgCl powder and chloroplatinic acid H
2PdCl
6Join in the distilled water, and vigorous stirring, make even dispersion obtain mixed liquor;
Step (2): to 6.8-7.0, in this mixed liquor, drip NaBH with KOH solution regulating step (1) gained pH of mixed value
3(CN) ethanolic solution is constant to the solution color and luster;
Step (3): vigorous stirring under the room temperature, centrifugation precipitation, and with the distilled water washing precipitation until no chlorion, 110 ℃ times dryings, obtain visible-light photocatalyst Pd/AgCl at last.
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| CN104785253A (en) * | 2015-05-09 | 2015-07-22 | 南昌航空大学 | Plasma photocatalyst and preparation method thereof |
| CN104959155A (en) * | 2015-06-03 | 2015-10-07 | 河北科技大学 | Nanometer copper/cuprous halide composite material and its preparation method and use |
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| CN104959155B (en) * | 2015-06-03 | 2017-10-27 | 河北科技大学 | Nanometer Copper/cuprous halide composite, preparation method and applications |
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| CN112979441A (en) * | 2019-12-13 | 2021-06-18 | 河北科技大学 | Method for chlorinating saturated C-H by using brine as chlorinating agent |
| CN112979441B (en) * | 2019-12-13 | 2022-10-25 | 河北科技大学 | Method for chlorinating saturated C-H by using brine as chlorinating agent |
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