CN1552524A - Selective oxidative light catalyst and preparing method thereof - Google Patents
Selective oxidative light catalyst and preparing method thereof Download PDFInfo
- Publication number
- CN1552524A CN1552524A CNA031409164A CN03140916A CN1552524A CN 1552524 A CN1552524 A CN 1552524A CN A031409164 A CNA031409164 A CN A031409164A CN 03140916 A CN03140916 A CN 03140916A CN 1552524 A CN1552524 A CN 1552524A
- Authority
- CN
- China
- Prior art keywords
- molecular sieve
- catalyst
- metal
- ion
- organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Catalysts (AREA)
Abstract
A photocatalyst for selective oxidization is prepared from the inorganic carrier including NaX and NaY molecular sieves, ZSM-5 molecular sieve, mesopore molecular sieve, SO2, and Al2O3, the transition metal ions chosen from Fe, Mn, Ni and Co and the organic ligand chosen from alpha, alpha'-bipyridine, 1-(2-pyridineazo)-2-naphthol (PAN), schiff base, etc through complexing.
Description
Technical field
The present invention relates to a kind of photochemical catalyst, relate in particular to a kind of photochemical catalyst of selective oxidation.
The invention still further relates to the preparation method of above-mentioned photochemical catalyst.
Background technology
Along with the continuous development of world technology, environmental protection and sustainable development more and more come into one's own.In the organic synthesis field, green oxidation has caused widely especially as a kind of environmental friendliness research direction to be paid close attention in recent years.So-called green oxidation just is meant utilizes hydrogen peroxide or molecular oxygen as oxidant, the oxidation reaction of utilizing water or other non-toxic compounds to realize for prerequisite as solvent, if can be under temperate condition, utilize the solar energy of cleaning to make the molecular oxygen activation of dissolving in the solution, realize variously having that huge applications is worth and the oxidizing process of potential value ideal more then, this be because: (1) solar energy and molecular oxygen all are the most cheap, and the energy that is easy to get and resource; (2) it is comparatively gentle that photochemical reaction is compared the reaction condition that thermodynamical reaction requires, and general normal temperature and pressure gets final product down; (3) photochemically reactive reactions steps is less, thereby has reduced the generation of accessory substance.In nearest research report, some semi-conducting materials are TiO for example
2, ZrO
2, ZnO, V
2O
5, SnO
2, Sb
2O
4, or the metal oxide of modified can realize the oxidation of out-phase photocatalysis alkene, but these catalyst can only utilize the ultraviolet light of wavelength less than 400nm, and ultraviolet light only account for solar spectrum less than 10%, this just causes the utilization rate of sunshine to reduce greatly.And on the other hand, some bionical systems, such as ferriporphyrin, iron-phthalocyanine, and some other metal complex, they have very big molar extinction coefficient at visible region, and are proved to be and have a visible light photocatalysis active.This type of document has the inventor to be published in " German applied chemistry " 2001,40, the article of 3014-3016 " the iron-phthalocyanine efficient oxidation degradable organic pollutant of excited by visible light " (X.Tao, W.Ma, T.Zhang, J.Zhao, Efficient oxidative degradation of organic pollutants in the presence of irontetrasulfophthalayanine under visible irradiation, Angew.Chem.Int.Ed.Engl., 2001,40,3014) and be published in " Europe chemistry " 2002,8, the article of 1321-1326 " a kind of new method of under visible light, using organic pollution in the iron-phthalocyanine catalytic degradation water " (X.Tao, W.Ma, T.Zhang, J.Zhao, A novel approach for the oxidative degradation oforganic pollutants in aqueous solutions mediated by irontetrasulfophthalocyanine under visible light radiation, Chem.Eur.J.2002,8,1321-1326).But hydrogen peroxide is necessary in this individual system, and turn over number is relatively low, and concerning homogeneous reaction system catalyst recovery and reuse difficult with the operation.Other utilize the system of visible light catalyst activate molecular oxygen to also have some loaded catalysts, Chinese patent application number: 01118066.8, " a kind of bionic visible light solid-phase catalyst and preparation method thereof ", the complex compound of metal is loaded on the cationic ion-exchange resin, in the activity that has shown good visible light photocatalysis and activate molecular oxygen aspect the oxidative degradation of pollutant.This type of document has the inventor to be published in " German applied chemistry " 2003,42, the article of 1029-1032 " the bipyridyl ironwork oxygen of excited by visible light is degradable organic pollutant effectively " (W.Ma, J.Li, X.Tao, J.He, Y.Xu, J.C.Yu, J.Zhao, Efficient degradation of organic pollutants by using dioxygen activatedby resin-exchanged iron (II) bipydine under visible irradiation, Angew.Chem.Int.Ed.Engl., 2003,42, demonstrate good photocatalytic activity after 1029-1032) bipyridyl iron loads on the resin in this system, and can be by the organic pollution in the activate molecular oxygen oxidative degradation water, but in this system, reactive intermediate is a non-selectivity, and the mineralising of organic molecule is main process, average 60% organic carbon has changed into carbon dioxide at last, this is disadvantageous for organic synthesis, and the less stable of resin own, and long-term illumination is easily aging.And the carrier molecule sieve not only has stronger stability, and the microenvironment of its uniqueness can make the oxidation of substrate molecule produce selectivity.In view of this advantage of molecular sieve, the scientific worker has carried out a large amount of research to it.This type of document has on " nature " magazine 1994,369, the article of 543-546 " molecular sieve carried manganese complex is the selection of catalysts olefin oxidation " (P.Gerrit, D.D.Vos, F.T.Starzyk, P.A.Jacobe, Zeolite-encapsulated Mn (II) complexes as catalysts forselective alkene oxidation, Nature, 1994,369,543-546) and " nature " magazine on 1994,370,541-544 " by the bionic catalyst of the effective cytochrome p-450 of a class of the molecular sieve carried iron complex preparation that is encapsulated in the high-polymer membrane phase " (An efficient mimic ofcytochrome P-450 from a zeolite-encaged iron complex in a polymermembrane, R.F.Perton, I.F.J.Vankelecom, M.J.A.Casselman, et.al., Nature, 1994,370,541-544).But these bionic catalysis systems all are the dark reaction systems, have also only only possessed the character of monooxygenase at present, promptly must realize catalytic cycle with elemental oxygens such as hydrogen peroxide.
Summary of the invention
The present invention loads to inorganic carrier molecular sieve or SiO with some metal complexs
2, Al
2O
3On, thereby under radiation of visible light, can reach the organic purpose of photo catalytic activation molecular oxygen selective oxidation.(420～580nm) have higher molar absorption coefficient (molar absorption coefficient ε to these metal complexs at visible region
(λ 510nm)～1.0 * 10
4Liter/mole centimetre), but its homogeneous phase excitation state is the poor ability of active dissolution oxygen molecule at ambient temperature, if it is its mode with bonding is immobilized to suitable molecular sieve, find at ambient temperature, (λ＞420nm) irradiation can activate dissolved molecular oxygen with very high efficient (turn over number TON＞10) to utilize visible light, optionally make organic matter (as: peacock green (MG), the styrene of body in mutually, cyclohexene etc.) in the oxidation down of nearly neutral pH value scope (4～9), oxidation rate and illumination are penetrated intensity and are directly proportional.Through recycling more than tens times, do not find that catalytic activity obviously reduces.The proportioning of substrate and catalyst is: 4～200mmol substrate: the 1g catalyst.
The scientific meaning of biomimetic photocatalysis agent of the present invention and range of application:
This life-span of excitation state in homogeneous system of the metal complex that the present invention chooses is shorter, generally do not have photocatalytic activity, and when it being loaded on a certain solid dielectric, the photochemical properties that is embodied is wonderful.These metal complexs by excited by visible light after, its excitation state combines with molecular oxygen and generates super oxygen intermediate, further then oxidation substrates.The advantage of this system maximum is water as solvent, and air or oxygen is as oxidant, so still not eco-friendly system, and greatly reduce reaction cost.This reaction has high selectivity, and product is more single, and this photochemical catalyst can be under the reaction condition of gentleness, and promptly normal temperature reacts under normal pressure, pH are closely neutral, can be made full use of and account for 90% visible light in the sunshine by excited by visible light again.Biomimetic photocatalysis agent of the present invention relatively is applicable to the substrate of molecular size less than 13 , substrate enters in the duct of molecular sieve, react with the active oxygen species of complex central transition metal ionic photo activated, this has just been avoided the process of phase transfer, makes the efficient of reaction increase.
The present invention finds and has verified a kind of photocatalytic activity of biomimetic photocatalysis agent.The key technology main points of invention are to have designed the concrete approach of activate molecular oxygen, by screening a metalloid organic coordination compound, make a concerted effort based on the strong bond that has between metal organic complex and the molecular sieve, it is immobilized to molecular sieve by the optimum molar ratio to have the metal organic complex that absorbs visible light characteristic, be prepared into and on catalytic performance, be different from the solid type biomimetic photocatalysis agent of homogeneous phase metal organic complex fully, light-catalyzed reaction system under the temperate condition is become a kind ofly carry out in the solid-liquid two-phase, need not use oxidants such as hydrogen peroxide, metal organic complex is efficient near zero-emission, easy flowing process system.Because selected molecular sieve has special microenvironment structure, and photochemical catalyst and substrate are concentrated in the cage of an optimum response environment, has greatly promoted the reaction probability, thereby has improved photocatalytic activity.
Photochemical catalyst provided by the invention, carrier are NaY or NaX type molecular sieve, ZSM-5 molecular sieve, mesoporous molecular sieve, SiO
2And Al
2O
3
Metal organic complex is that transition metal ions cooperates by coordinate bond with nitrogenous or hydroxyl organic ligand and forms;
Described transition metal ions is divalence or ferric ion, divalence cobalt manganese nickel ion;
Described organic compound/metal ion mole match ratio is 3-2: 1;
Mole/the mass ratio of organic cooperation ion of described metal and molecular sieve carrier is 10
-6～10
-2Moles per gram.
Described metal organic complex is α, α '-bipyridyl, 1,10-Phen, 1-(2-pyridylazo)-beta naphthal (PAN) or schiff bases.
The method of the above-mentioned photochemical catalyst of preparation provided by the invention, undertaken by following step:
A) pre-treatment of molecular screen material
Adopt conventional method, molecular sieve carrier is carried out pickling and alkali cleaning after, with water rinse to neutral, drying for standby;
B) preparation of metal ion solution
Earlier watery hydrochloric acid, nitric acid or the sulfuric acid solution of preparation 0.1～0.5mol/L add water miscible divalence or trivalent iron salt, water miscible divalence cobalt nickel manganese salt, stirring and dissolving according to the solid-to-liquid ratio of 10～50 grams per liters then;
C) load of metal ion
The metal ion solution of preparation is dropped in the molecular sieve, stir;
D) processing of loaded metal ion molecular sieve
With the molecular sieve centrifugation that step C makes, add entry and stir, supernatant liquor is removed in sedimentation, adds water washing for several times, and after the centrifugation, normal temperature is dry down;
E) complexing of part
The organic compound part is mixed with the molecular sieve that step D makes in molar ratio, grind, place in the closed reactor, nitrogen protection in 70-90 ℃, is reacted reactor to take out standby in 4-30 hour;
F) purifying of catalyst
The catalyst that step e makes is wrapped with filter paper, placed in the apparatus,Soxhlet's, use CH
2Cl
2Or acetone adds hot reflux 4-30 hour as solvent, 40-60 ℃ of the following heating of nitrogen, dry 5-15 hour.
Photochemical catalyst purposes of the present invention:
Photochemical catalyst of the present invention can be used for the light-catalyzed reaction in fields such as selectivity organic photosynthetic one-tenth, bionical light compositing, biology/microbial project, biological selectivity pharmacy and physiochemistry.
Description of drawings
Fig. 1, peacock green dyestuff 2 * 10
-5M visible light (the photocatalysis oxidation reaction result under the irradiation of λ＞420nm), wherein:
Curve 1: dark reaction.0.05 1/ liter in gram sample (by preparation among the embodiment 1).
Curve 2:0.05 gram control sample/liter (by implementing preparation in the reference examples 1).
Curve 3:0.05 gram sample 1/ liter (by preparation among the embodiment 1) fills helium.
1/ liter in curve 4:0.05 gram sample (by preparation among the embodiment 1).
Fig. 2, continuous 4 the circulation degraded peacock green dyestuffs (each 2 * 10 of catalyst
-5M) photocatalytic activity result, wherein:
Curve 1: reactant concentration changes, 1/ liter in 0.05 gram sample (sample 1 is by preparation among the embodiment 1).
Curve 2: production concentration changes, 1/ liter in 0.05 gram sample (sample 1 is by preparation among the embodiment 1).
The specific embodiment
Specify effect of the present invention below in conjunction with accompanying drawing.
Get selected 10 gram molecules sieve, join in the reactor through after giving processing, ferrous chloride (FeCl
24H
2O) be made into 2 * 10
-30.5 liter of the aqueous solution of M, stirring makes the metal ion load complete more than 5 hours.Water continues to wash drying for standby behind the no iron ion.With α, α '-bipyridyl 2 grams mix the abundant grinding in back with the molecular sieve for preparing after, place in the closed container, be heated to 90 ℃ of reactions 24 hours at tube furnace.The crude product that makes is wrapped with filter paper, used CH
2Cl
2Make solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's.
Make the ferrous molecular sieve of load 10 grams with embodiment 1, and take by weighing 1 in addition, 10-phenanthroline (C
12H
8N
2H
2O) 3 grams after mixing, place in the closed container, are heated to 90 ℃ of reactions 24 hours at tube furnace.The crude product that makes is wrapped with filter paper, made solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's with acetone.
Make ferrous molecular sieve 10 grams of load with embodiment 1, restrain, after mixing, place in the closed container, be heated to 90 ℃ of reactions 24 hours at tube furnace with taking by weighing schiff bases 2 in addition.The crude product that makes is wrapped with filter paper, used CH
2Cl
2Make solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's.
With manganese nitrate Mn (NO
3)
2Be made into 2 * 10
-30.5 liter of the aqueous solution of M.Add 10 gram molecules sieve, stirring makes the metal ion load complete more than 5 hours.Water continues to wash drying for standby behind the no manganese ion.With α, α '-bipyridyl 2 grams mix the abundant grinding in back with the molecular sieve for preparing after, place in the closed container, be heated to 100 ℃ of reactions 24 hours at tube furnace.The crude product that makes is wrapped with filter paper, used CH
2Cl
2Make solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's.
With cobaltous sulfate (CoSO
47H
2O) be made into 2 * 10
-30.5 liter of the aqueous solution of M.Add 10 gram molecules sieve, stirring makes the metal ion load complete more than 5 hours.Water continues to wash drying for standby behind the no cobalt ions, and takes by weighing schiff bases 2 grams in addition, after mixing, places in the closed container, is heated to 100 ℃ of reactions 24 hours at tube furnace.The crude product that makes is wrapped with filter paper, made solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's with acetone.
With nickel nitrate NiNO
3Be made into 2 * 10
-30.5 liter of the aqueous solution of M.Add 10 gram molecules sieve, stirring makes the metal ion load complete more than 5 hours.Water continues to wash drying for standby behind the non-nickle ion.With α, α '-bipyridyl 2 grams mix the abundant grinding in back with the molecular sieve for preparing after, place in the closed container, be heated to 100 ℃ of reactions 24 hours at tube furnace.The crude product that makes is wrapped with filter paper, used CH
2Cl
2Make solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's.
Embodiment 7
With ferrous chloride (FeCl
24H
2O) be made into 2 * 10
-40.2 liter of the aqueous solution of M.Add 10 gram SiO
2, stirring makes the metal ion load complete more than 5 hours.Water continues to wash drying for standby behind the no iron ion.With α, α '-bipyridyl 0.5 gram and the SiO for preparing
2After mixing the abundant grinding in back, place in the closed container, be heated to 90 ℃ of reactions 24 hours at tube furnace.The crude product that makes is wrapped with filter paper, used CH
2Cl
2Make solvent, remove unnecessary part, under nitrogen protection, can use after 50 ℃ of dryings of heating with apparatus,Soxhlet's.
Reference examples 1
With molecular sieve 10 grams of choosing, handle the back adding with ferrous chloride (FeCl through giving
24H
2O) be made into 2 * 10
-30.5 liter of the aqueous solution of M carries out the bonding load, stirs to make the ferrous ion load complete.Water continues to wash, and does not contain till the iron ion in supernatant.Can use after the drying.
Claims (3)
1, a kind of photochemical catalyst of selective oxidation, carrier are NaY or NaX type molecular sieve, ZSM-5 molecular sieve, mesoporous molecular sieve, SiO
2And Al
2O
3
Metal organic complex is that transition metal ions cooperates by coordinate bond with nitrogenous or hydroxyl organic ligand and forms;
Described transition metal ions is divalence or ferric ion, divalence cobalt manganese nickel ion;
Described organic compound/metal ion mole match ratio is 3-2: 1;
Mole/the mass ratio of organic cooperation ion of described metal and molecular sieve carrier is 10
-6～10
-2Moles per gram.
2, photochemical catalyst as claimed in claim 1 is characterized in that, described metal organic complex is α, α '-bipyridyl, 1,10-Phen, 1-(2-pyridylazo)-beta naphthal (PAN) or schiff bases.
3, a kind of preparation method of photochemical catalyst as claimed in claim 1 or 2, undertaken by following step:
A) pre-treatment of molecular screen material
Adopt conventional method, molecular sieve carrier is carried out pickling and alkali cleaning after, with water rinse to neutral, drying for standby;
B) preparation of metal ion solution
Earlier watery hydrochloric acid, nitric acid or the sulfuric acid solution of preparation 0.1～0.5mol/L add water miscible divalence or trivalent iron salt, water miscible divalence cobalt nickel manganese salt, stirring and dissolving according to the solid-to-liquid ratio of 10～50 grams per liters then;
C) load of metal ion
The metal ion solution of preparation is dropped in the molecular sieve, stir;
D) processing of loaded metal ion molecular sieve
With the molecular sieve centrifugation that step C makes, add entry and stir, supernatant liquor is removed in sedimentation, adds water washing for several times, and after the centrifugation, normal temperature is dry down;
E) complexing of part
The organic compound part is mixed with the molecular sieve that step D makes in molar ratio, grind, place in the closed reactor, nitrogen protection in 70-90 ℃, is reacted reactor to take out standby in 4-30 hour;
F) purifying of catalyst
The catalyst that step e makes is wrapped with filter paper, placed in the apparatus,Soxhlet's, use CH
2Cl
2Or acetone adds hot reflux 4-30 hour as solvent, 40-60 ℃ of the following heating of nitrogen, dry 5-15 hour.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031409164A CN1552524A (en) | 2003-06-05 | 2003-06-05 | Selective oxidative light catalyst and preparing method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031409164A CN1552524A (en) | 2003-06-05 | 2003-06-05 | Selective oxidative light catalyst and preparing method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1552524A true CN1552524A (en) | 2004-12-08 |
Family
ID=34323931
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA031409164A Pending CN1552524A (en) | 2003-06-05 | 2003-06-05 | Selective oxidative light catalyst and preparing method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1552524A (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388979C (en) * | 2005-04-19 | 2008-05-21 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN100493713C (en) * | 2006-09-25 | 2009-06-03 | 中国科学院化学研究所 | Visible light photocatalyst for constructing non-nitrogen and iron complex with hydrogen-like quinone and uses of the same |
| CN100531911C (en) * | 2005-10-25 | 2009-08-26 | 中国科学院化学研究所 | Solid phase catalytic auxiliary and its preparation method and use |
| CN100560492C (en) * | 2006-11-09 | 2009-11-18 | 中国科学院大连化学物理研究所 | A kind of difunctionalization mesopore silica material and preparation method and application |
| CN101049571B (en) * | 2007-05-17 | 2010-05-19 | 南京工业大学 | Complex type molecular sieve catalyst, preparation method, and application in preparing crylic acid |
| CN101518742B (en) * | 2009-04-08 | 2011-10-19 | 中国科学院化学研究所 | Iron composition visible light photocatalyst composed of double-coordination functional group ligands and iron ions and preparation method and purpose thereof |
| CN103086866A (en) * | 2013-02-19 | 2013-05-08 | 中国科学院化学研究所 | Method for synthesizing acid by oxidizing aldehyde in photocatalytic selective mode |
| CN104907097A (en) * | 2014-03-10 | 2015-09-16 | 江苏瑞丰科技实业有限公司 | Room temperature efficient carbon monoxide removing catalysis material |
| CN108609714A (en) * | 2018-03-21 | 2018-10-02 | 四川大学 | A method of removing incretion interferent in water removal using carbon-based magnetic metal composite material catalyzing activation persulfate |
| CN108654661A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院大连化学物理研究所 | A kind of SO2Electrochemical oxidation non-precious metal catalyst and its preparation and application |
| CN108722490A (en) * | 2018-05-22 | 2018-11-02 | 北京理工大学 | A kind of metal bipyridine salt photochemical catalyst, preparation method and applications |
| CN108864436A (en) * | 2018-05-28 | 2018-11-23 | 桂林电子科技大学 | A kind of novel cobalt complex crystalline material preparation method and application |
| CN111185224A (en) * | 2020-02-24 | 2020-05-22 | 东南大学 | CO (carbon monoxide)2Process for preparing aromatization catalyst |
| CN112645975A (en) * | 2020-11-04 | 2021-04-13 | 重庆顺泽生物技术研究院有限公司 | Silicon-phenanthroline derivatives, preparation and use thereof |
| CN114870899A (en) * | 2022-04-02 | 2022-08-09 | 中国科学院青岛生物能源与过程研究所 | Photocatalytic CO 2 Composite photocatalyst for preparing synthesis gas by decomposition and preparation method thereof |
-
2003
- 2003-06-05 CN CNA031409164A patent/CN1552524A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100388979C (en) * | 2005-04-19 | 2008-05-21 | 中国科学院化学研究所 | Method for degrading organic pollutant by light catalyst and its special solid-phase light catalyst |
| CN100531911C (en) * | 2005-10-25 | 2009-08-26 | 中国科学院化学研究所 | Solid phase catalytic auxiliary and its preparation method and use |
| CN100493713C (en) * | 2006-09-25 | 2009-06-03 | 中国科学院化学研究所 | Visible light photocatalyst for constructing non-nitrogen and iron complex with hydrogen-like quinone and uses of the same |
| CN100560492C (en) * | 2006-11-09 | 2009-11-18 | 中国科学院大连化学物理研究所 | A kind of difunctionalization mesopore silica material and preparation method and application |
| CN101049571B (en) * | 2007-05-17 | 2010-05-19 | 南京工业大学 | Complex type molecular sieve catalyst, preparation method, and application in preparing crylic acid |
| CN101518742B (en) * | 2009-04-08 | 2011-10-19 | 中国科学院化学研究所 | Iron composition visible light photocatalyst composed of double-coordination functional group ligands and iron ions and preparation method and purpose thereof |
| CN103086866A (en) * | 2013-02-19 | 2013-05-08 | 中国科学院化学研究所 | Method for synthesizing acid by oxidizing aldehyde in photocatalytic selective mode |
| CN104907097A (en) * | 2014-03-10 | 2015-09-16 | 江苏瑞丰科技实业有限公司 | Room temperature efficient carbon monoxide removing catalysis material |
| CN104907097B (en) * | 2014-03-10 | 2018-05-15 | 江苏瑞丰科技实业有限公司 | Normal-temperature efficient removes catalyzing carbon monoxide material |
| CN108654661A (en) * | 2017-04-01 | 2018-10-16 | 中国科学院大连化学物理研究所 | A kind of SO2Electrochemical oxidation non-precious metal catalyst and its preparation and application |
| CN108609714A (en) * | 2018-03-21 | 2018-10-02 | 四川大学 | A method of removing incretion interferent in water removal using carbon-based magnetic metal composite material catalyzing activation persulfate |
| CN108609714B (en) * | 2018-03-21 | 2020-07-24 | 四川大学 | Method for removing endocrine disruptors in water by catalytically activating persulfate through carbon-based magnetic metal composite material |
| CN108722490A (en) * | 2018-05-22 | 2018-11-02 | 北京理工大学 | A kind of metal bipyridine salt photochemical catalyst, preparation method and applications |
| CN108864436A (en) * | 2018-05-28 | 2018-11-23 | 桂林电子科技大学 | A kind of novel cobalt complex crystalline material preparation method and application |
| CN108864436B (en) * | 2018-05-28 | 2020-09-22 | 桂林电子科技大学 | Preparation method and application of novel cobalt complex crystal material |
| CN111185224A (en) * | 2020-02-24 | 2020-05-22 | 东南大学 | CO (carbon monoxide)2Process for preparing aromatization catalyst |
| CN111185224B (en) * | 2020-02-24 | 2022-04-12 | 东南大学 | CO (carbon monoxide)2Process for preparing aromatization catalyst |
| CN112645975A (en) * | 2020-11-04 | 2021-04-13 | 重庆顺泽生物技术研究院有限公司 | Silicon-phenanthroline derivatives, preparation and use thereof |
| CN114870899A (en) * | 2022-04-02 | 2022-08-09 | 中国科学院青岛生物能源与过程研究所 | Photocatalytic CO 2 Composite photocatalyst for preparing synthesis gas by decomposition and preparation method thereof |
| CN114870899B (en) * | 2022-04-02 | 2023-11-07 | 中国科学院青岛生物能源与过程研究所 | Photocatalytic CO 2 Composite photocatalyst for decomposing and preparing synthetic gas and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1552524A (en) | Selective oxidative light catalyst and preparing method thereof | |
| Zhang et al. | One-step hydrothermal synthesis of CdxInyS (x+ 1.5 y) for photocatalytic oxidation of biomass-derived 5-hydroxymethylfurfural to 2, 5-diformylfuran under ambient conditions | |
| CN105478155B (en) | A kind of renewable heterogeneous Fenton type catalyst and its preparation method and application | |
| CN102527420B (en) | Preparation method of bismuth subcarbonate photocatalyst | |
| CN109675581B (en) | Ferro-manganese bimetal oxide modified biochar photo-Fenton composite material and preparation method thereof | |
| Chen et al. | Studies on the photocatalytic performance of cuprous oxide/chitosan nanocomposites activated by visible light | |
| CN102078807B (en) | Er<3+>:YAlO3/TiO2-loaded photocatalyst and preparation method thereof | |
| CN110433821A (en) | A kind of preparation method of ferrimanganic double-metal composite catalyst and its application in industrial waste water purifying | |
| CN102941084A (en) | Method for preparing double-component metallic oxide catalytic ozonation catalyst | |
| CN106865685B (en) | Treatment method for photocatalytic degradation of rhodamine B dye wastewater | |
| Zhang et al. | The marriage of ferrocene and silicotungstate: an ingenious heterogeneous Fenton-like synergistic photocatalyst | |
| CN105013518B (en) | A kind of preparation method for the ozone oxidation composite catalyst that visible ray for wastewater treatment is strengthened | |
| CN109590027B (en) | MoS2Reinforced heterogeneous Fenton photocatalyst and preparation method thereof | |
| CN110639620A (en) | Composite photocatalyst for degrading tetracycline and preparation method and application thereof | |
| CN110813349A (en) | Binary metal oxide composite carbon nitride catalyst and preparation method and application thereof | |
| CN108355669A (en) | A kind of magnetic Nano onion carbon load Bi2WO6Photochemical catalyst and its preparation method and application | |
| CN100460067C (en) | Composite bismuth vanadium photocatalyst supported by nickel oxide and preparation method thereof | |
| CN102389836B (en) | Polyaniline/titanium dioxide/clay nanometer composite photocatalyst and preparation method thereof | |
| CN112718008A (en) | Heterogeneous photosensitizer based on metal organic framework material as carrier and preparation method and application thereof | |
| CN108079993A (en) | The preparation method of ferrous oxide/cuprous nano composite material | |
| An et al. | Electron transfer mechanism that Ti3C2 regulates Cl-doped carbon nitride nanotube: Realizing efficient photocatalytic decarbonization and denitrification in wastewater | |
| CN111229200B (en) | Bismuth oxide modified Ti 3+ Self-doping TiO 2 Preparation method of heterojunction photocatalyst | |
| CN105170115A (en) | Preparation method and applications of ternary polyaniline-titanium dioxide-hollow bead composite nano material | |
| CN1118328C (en) | Bionic visible light solid-phase catalyst and its preparing process | |
| CN110180546A (en) | A kind of catalyst and preparation method thereof for nature light processing waste water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |