CN112076776B - Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof - Google Patents
Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof Download PDFInfo
- Publication number
- CN112076776B CN112076776B CN202011003614.7A CN202011003614A CN112076776B CN 112076776 B CN112076776 B CN 112076776B CN 202011003614 A CN202011003614 A CN 202011003614A CN 112076776 B CN112076776 B CN 112076776B
- Authority
- CN
- China
- Prior art keywords
- carbon nitride
- protonated
- alcohol
- protonated carbon
- solid powder
- 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.)
- Active
Links
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 24
- 230000003647 oxidation Effects 0.000 title claims abstract description 23
- 150000002148 esters Chemical class 0.000 title claims abstract description 16
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 15
- -1 Protonated carbon nitrides Chemical class 0.000 title claims abstract description 12
- 150000001298 alcohols Chemical class 0.000 title description 9
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical class N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 82
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims abstract description 51
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 39
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 claims abstract description 20
- 235000019445 benzyl alcohol Nutrition 0.000 claims abstract description 17
- 239000002253 acid Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229940095102 methyl benzoate Drugs 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000011941 photocatalyst Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 4
- 230000001590 oxidative effect Effects 0.000 claims abstract description 4
- 239000000843 powder Substances 0.000 claims description 44
- 239000007787 solid Substances 0.000 claims description 33
- 238000000227 grinding Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 239000002243 precursor Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical group NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 15
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 150000003839 salts Chemical class 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 238000012719 thermal polymerization Methods 0.000 abstract description 2
- 238000005303 weighing Methods 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- FPHQLDRCDMDGQW-UHFFFAOYSA-N iridium Chemical compound [Ir].[Ir] FPHQLDRCDMDGQW-UHFFFAOYSA-N 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid group Chemical group C(C1=CC=CC=C1)(=O)O WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000005711 Benzoic acid Substances 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 238000006709 oxidative esterification reaction Methods 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
- C07C67/40—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of primary alcohols
Abstract
The invention discloses protonated carbon nitride and application of the protonated carbon nitride as a photocatalyst in selective oxidation of alcohol to generate ester, and belongs to the technical field of photocatalytic organic synthesis. The protonated carbon nitride is prepared by synthesizing bulk-phase carbon nitride by a thermal polymerization method, treating the bulk-phase carbon nitride by a molten salt method to obtain molten salt carbon nitride, and reacting the molten salt carbon nitride with acid. The protonated carbon nitride is used as a photocatalyst, oxygen can be used as an oxidant under the irradiation of visible light with the wavelength of 420nm, and the protonated carbon nitride can efficiently catalyze the reaction of benzyl alcohol and methanol to generate methyl benzoate, so that the method has an important application prospect.
Description
Technical Field
The invention belongs to the technical field of photocatalytic organic synthesis, and particularly relates to protonated carbon nitride and application of the protonated carbon nitride as a photocatalyst in selective oxidation of alcohol to generate ester.
Background
Ester compounds are a class of abundant and highly important chemical substances, and are widely applied to the fields of polymers, natural products, medicines and other fine chemical engineering. Generally, esters are prepared by reacting carboxylic acids or reactive acid derivatives with alcohols, and although this process is widely used in industrial and scientific laboratories, the process steps are cumbersome and often result in the formation of large amounts of unwanted by-products. To break through this limitation, in recent years, scientists have developed a number of strategies for synthesizing esters. For example, oxidative esterification of aldehydes is an effective method for preparing esters. However, this method requires a metal salt as an oxidizing agent or a noble metal as a catalyst: (Nat. Chem.2010, 2, 61), which does not meet the original intention of green chemistry. Thus, develop aThe preparation method of the ester compound which is environment-friendly and has low cost is very significant.
Alcohol compounds can be prepared from renewable biomass, are environmentally friendly and abundant, and are often used as solvents and substrates for various chemical reactions. In various alcohol conversion reactions, the direct oxidation of alcohols to esters using oxygen is clearly attractive. To date, there have been only few studies on the direct esterification of alcohols, most of which are based on homogeneous catalytic systems, requiring noble metal-based catalysts, such as palladium (a), (b), (c), (d), and (d)Org. Lett.2013, 15, 5072), ruthenium (A)Angew. Chem., Int. Ed.2012, 51, 5711), gold (J. Am. Chem. Soc2010, 132, 15096), and iridium (iridium) (iridium: (iridium) (2010, 132) (15096) (iridium) (2010, and (iridium) (2010, 132) (iridium) (J. Org. Chem.2011, 76, 2937). Moreover, these homogeneous catalytic systems require the addition of a base to neutralize the acid generated during the process, and generally need to be carried out at high temperatures and pressures in order to obtain higher yields. In general, heterogeneous catalysis is advantageous over homogeneous catalysis because the catalyst is easily separated from the reaction mixture and can be effectively recycled. Therefore, it is attractive and challenging to develop a heterogeneous, cheap and easily available catalyst for efficiently catalyzing the oxidation of alcohol compounds to ester compounds.
As an important non-metallic material, polymeric carbon nitride is of great interest due to its unique properties, particularly visible light response and excellent chemical stability (C: (C))Angew. Chem. Int. Ed., 2019, 58, 6164). These properties have led to the widespread use of carbon nitride in heterogeneous organic synthesis reactions. In the reported selective oxidation reactions of alcohols involving carbon nitride, the product is usually an aldehyde rather than an ester (C: (C) (R))Chem. Sci., 2013, 4, 3244). So far, there is no report of direct oxidation of alcohols to esters without adding a metal-containing carbon nitride catalyst. The present invention uses an acid to treat carbon nitride to obtain protonated carbon nitride. The method not only retains the better oxidation capability of the fused salt carbon nitride, but also introduces an acid site on the surface, and can realize the high-efficiency oxidation of the benzyl alcohol and the methanol to generate the methyl benzoate under the conditions of oxygen and illumination.
Disclosure of Invention
The invention aims to provide protonated carbon nitride and a method for selectively oxidizing alcohol to generate ester by using the protonated carbon nitride as a photocatalyst. The protonized carbon nitride prepared by the method overcomes the defect of weak oxidation capability of the traditional carbon nitride, and can realize the high-efficiency oxidation of benzyl alcohol and methanol to generate methyl benzoate.
In order to achieve the purpose, the invention adopts the following technical scheme:
a protonized carbon nitride for selective photocatalytic oxidation of alcohol to ester is prepared through thermal polymerization to obtain bulk-phase carbon nitride, treating by molten-salt method to obtain molten-salt carbon nitride, and reacting with acid to obtain said protonized carbon nitride.
The preparation method of the protonated carbon nitride specifically comprises the following steps:
(1) placing the amine-containing solid powder in a crucible, and calcining for 10 hours at the temperature of 600 ℃ in an air atmosphere to obtain bulk-phase carbon nitride;
(2) placing the bulk-phase carbon nitride obtained in the step (1) and inorganic salt in a mortar according to the mass ratio of 1:3-6 for grinding to obtain molten salt carbon nitride;
(3) calcining the fused salt carbon nitride obtained in the step (2) for 12 hours at the temperature of 400-650 ℃ in a nitrogen atmosphere to obtain a sample precursor;
(4) washing off redundant inorganic salt in the sample precursor obtained in the step (3) by using deionized water, drying, putting into a beaker, adding acid liquor with the volume concentration of 20% according to the mass-to-volume ratio of 20:1 mg/mL, stirring overnight, centrifuging to remove liquid, and drying again to obtain the protonated carbon nitride.
In the step (1), the amine-containing solid powder is melamine, cyanamide or urea.
The inorganic salt in the step (2) comprises any one or more of sodium chloride, lithium chloride, potassium chloride, ammonium chloride and the like.
The acid solution used in the step (4) is an aqueous solution of inorganic acid such as sulfuric acid, hydrochloric acid or phosphoric acid.
The protonated carbon nitride can be used for selective photocatalytic oxidation of alcohol to generate ester, and specifically, the protonated carbon nitride is used as a photocatalyst, and under the irradiation of visible light with the wavelength of 420nm, oxygen is used as an oxidant to selectively catalyze benzyl alcohol to react with methanol to generate methyl benzoate.
The invention has the following remarkable advantages:
(1) the protonized carbon nitride prepared by the invention is a novel photocatalyst, the oxygen activation capability of the protonized carbon nitride is enhanced, and the efficient oxidation of benzyl alcohol and methanol to generate methyl benzoate can be realized.
(2) The invention has simple production process, easy control, low energy consumption and low cost, meets the actual production requirement and is beneficial to large-scale popularization.
Drawings
FIG. 1 is an XRD pattern of protonated carbon nitride from example 1.
FIG. 2 is a FT-IR chart of the protonated carbon nitride obtained in example 1.
FIG. 3 is an SEM photograph of protonated carbon nitride from example 1.
FIG. 4 is a TEM image of the protonated carbon nitride obtained in example 1.
FIG. 5 is a diagram showing the analysis of the composition of the solid powder of carbon nitride (a) and protonated carbon nitride (b) obtained in example 1 by the photocatalytic oxidation of benzyl alcohol and methanol.
FIG. 6 is a diagram showing the analysis of the components of the products of photocatalytic oxidation of benzyl alcohol and methanol by protonated carbon nitride obtained in example 2.
FIG. 7 is a graph showing the composition analysis of the products of photocatalytic oxidation of benzyl alcohol and methanol by protonated carbon nitride obtained in example 3.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
(1) Weighing 8 g of melamine solid powder, placing the melamine solid powder into an alumina crucible, calcining for 10 hours at 410 ℃ in air atmosphere, naturally cooling, taking out, and grinding into powder to obtain bulk-phase carbon nitride solid powder;
(2) weighing 1 g of bulk-phase carbon nitride solid powder and 4.0 g of lithium chloride, uniformly grinding, placing into an alumina crucible, calcining for 12 hours at 600 ℃ in a nitrogen atmosphere, naturally cooling, taking out, grinding into powder, washing with deionized water, removing residual lithium chloride by a suction filtration method, and then placing the obtained sample into an oven for drying to obtain carbon nitride solid powder;
(3) weighing 500 mg of carbon nitride solid powder, placing the carbon nitride solid powder in a beaker, adding 20 ml of deionized water and 5 ml of concentrated hydrochloric acid, stirring overnight, centrifuging to remove liquid, and drying a centrifuged sample to obtain protonated carbon nitride solid powder.
FIG. 1 is an XRD pattern of protonated carbon nitride obtained in this example. As can be seen from the figure, the protonated carbon nitride solid powder has two obvious XRD diffraction peaks at 8 degrees and 27.5 degrees, which are assigned to the (100) and (002) crystal faces of the polymer carbon nitride, and the prepared carbon nitride material is proved to have no obvious change in the crystal structure after being subjected to protonation treatment.
FIG. 2 is a FT-IR chart of the protonated carbon nitride obtained in this example.
Fig. 3 and 4 are SEM and TEM images of the protonated carbon nitride obtained in this example, respectively. As can be seen, the protonated carbon nitride samples are in a sheet-like, stacked structure and significant lattice striations are observed.
The obtained carbon nitride solid powder and the protonated carbon nitride solid powder were weighed 10 mg each, placed in a glass reactor having a volume of 10 ml, 1 ml of methanol and 0.2 mmol (about 22 μ l) of benzyl alcohol were added, respectively, oxygen was introduced, the mixture was reacted for 24 hours at 25 ℃ under 420nm LED illumination, and the reaction product was analyzed using a gas chromatography-mass spectrometer.
FIG. 5 is a diagram showing the analysis of the components of the carbon nitride solid powder (a) and the protonated carbon nitride (b) obtained in this example, which are obtained by photocatalytic oxidation of benzyl alcohol and methanol. As can be seen from the figure, the carbon nitride solid powder can catalyze the conversion of benzyl alcohol (conversion rate 99%), but the main product is benzoic acid (selectivity 99%), and the selectivity of methyl benzoate is very low (less than 1%); the protonated carbon nitride can not only catalyze the conversion of the benzyl alcohol well (the conversion rate is 99 percent), but also realize the high-efficiency selection of the methyl benzoate (the selectivity is 94 percent).
Example 2
(1) Weighing 8 g of cyanamide solid powder, placing the powder into an alumina crucible, calcining the powder for 10 hours at 300 ℃ in air atmosphere, naturally cooling the powder, taking the powder out, and grinding the powder into powder to obtain bulk-phase carbon nitride solid powder;
(2) weighing 1 g of bulk-phase carbon nitride solid powder and 5.0 g of potassium chloride, uniformly grinding, placing into an alumina crucible, calcining for 12 hours at 400 ℃ in a nitrogen atmosphere, naturally cooling, taking out, grinding into powder, washing with deionized water, removing residual potassium chloride by a suction filtration method, and then placing the obtained sample into an oven for drying to obtain carbon nitride solid powder;
(3) weighing 500 mg of carbon nitride solid powder, placing the carbon nitride solid powder in a beaker, adding 20 ml of deionized water and 5 ml of concentrated sulfuric acid, stirring overnight, centrifuging to remove liquid, and drying a centrifuged sample to obtain protonated carbon nitride solid powder.
FIG. 6 is a diagram showing the composition analysis of the products of photocatalytic oxidation of benzyl alcohol and methanol by protonated carbon nitride obtained in this example. As can be seen from the figure, the protonated carbon nitride can well catalyze the conversion of the benzyl alcohol (the conversion rate is 99%), and meanwhile, the methyl benzoate also has higher selectivity (the selectivity is 85%).
Example 3
(1) Weighing 8 g of urea solid powder, placing the urea solid powder into an alumina crucible, calcining for 10 hours at 600 ℃ in air atmosphere, naturally cooling, taking out, and grinding into powder to obtain bulk-phase carbon nitride solid powder;
(2) weighing 1 g of bulk-phase carbon nitride solid powder and 6.0 g of ammonium chloride, uniformly grinding, placing into an alumina crucible, calcining for 12 hours at 650 ℃ in a nitrogen atmosphere, naturally cooling, taking out, grinding into powder, washing with deionized water, removing the residual ammonium chloride by a suction filtration method, and then placing the obtained sample into an oven for drying to obtain carbon nitride solid powder;
(3) weighing 500 mg of carbon nitride solid powder, placing the carbon nitride solid powder in a beaker, adding 20 ml of deionized water and 5 ml of concentrated hydrochloric acid, stirring overnight, centrifuging to remove liquid, and drying a centrifuged sample to obtain protonated carbon nitride solid powder.
FIG. 7 is a diagram showing the composition analysis of the products of photocatalytic oxidation of benzyl alcohol and methanol by protonated carbon nitride obtained in this example. As can be seen from the figure, the catalytic conversion of protonated carbon nitride to benzyl alcohol is about 60% with methyl benzoate selectivity of 31%.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (3)
1. Use of protonated carbon nitride for selective photocatalytic oxidation of an alcohol to form an ester, characterized by: the protonated carbon nitride is used as a photocatalyst, and oxygen is used as an oxidant under the irradiation of visible light with the wavelength of 420nm to selectively catalyze the reaction of benzyl alcohol and methanol to generate methyl benzoate;
the preparation of the protonated carbon nitride comprises the following steps:
(1) placing the amine-containing solid powder in a crucible, and calcining for 10 hours at the temperature of 600 ℃ in an air atmosphere to obtain bulk-phase carbon nitride;
(2) putting the bulk-phase carbon nitride obtained in the step (1) and inorganic salt into a mortar according to a certain proportion, and grinding to obtain molten salt carbon nitride;
(3) calcining the fused salt carbon nitride obtained in the step (2) for 12 hours at the temperature of 400-650 ℃ in a nitrogen atmosphere to obtain a sample precursor;
(4) washing off redundant inorganic salt in the sample precursor obtained in the step (3) by water, drying, adding acid liquor, stirring overnight, centrifuging to remove liquid, and drying again to obtain the protonated carbon nitride;
the mass ratio of the bulk-phase carbon nitride to the inorganic salt used in the step (2) is 1: 3-6; the inorganic salt comprises one or more of sodium chloride, lithium chloride, potassium chloride and ammonium chloride.
2. Use of protonated carbon nitride according to claim 1 for selective photocatalytic oxidation of an alcohol to esters, characterized in that: in the step (1), the amine-containing solid powder is melamine, cyanamide or urea.
3. Use of protonated carbon nitride according to claim 1 for selective photocatalytic oxidation of an alcohol to esters, characterized in that: the mass-to-volume ratio of the sample precursor to the acid liquor used in the step (4) is 20:1 mg/mL;
the acid solution used has a volume concentration of 20% and is an aqueous solution of sulfuric acid, hydrochloric acid or phosphoric acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011003614.7A CN112076776B (en) | 2020-09-22 | 2020-09-22 | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011003614.7A CN112076776B (en) | 2020-09-22 | 2020-09-22 | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112076776A CN112076776A (en) | 2020-12-15 |
| CN112076776B true CN112076776B (en) | 2021-08-31 |
Family
ID=73739606
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011003614.7A Active CN112076776B (en) | 2020-09-22 | 2020-09-22 | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112076776B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113842938A (en) * | 2021-09-18 | 2021-12-28 | 河北零点新能源科技有限公司 | Novel g-C3N4Method for preparing derived carbonaceous adsorbent and photocatalytic material |
| CN113845096A (en) * | 2021-10-09 | 2021-12-28 | 浙江大学杭州国际科创中心 | Preparation method of cyano-rich carbon nitride, product and application thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107188294B (en) * | 2017-06-22 | 2019-10-15 | 武汉纺织大学 | A method of organic pollutant in catalysis percarbonate degrading waste water |
| CN107488133B (en) * | 2017-08-18 | 2019-08-09 | 福州大学 | A kind of method of carbonitride photocatalysis synthesis of carbamates class compound |
| CN108584892A (en) * | 2018-04-26 | 2018-09-28 | 福州大学 | A kind of preparation method and applications of crystalline phase azotized carbon nano particle |
| CN109985654B (en) * | 2019-04-26 | 2021-07-13 | 福州大学 | Alkali metal ion modified carbon nitride catalyst and preparation method and application thereof |
| CN111250140A (en) * | 2020-03-03 | 2020-06-09 | 武汉大学 | Carbon nitride nanorod array photocatalyst for photocatalytic nitrogen fixation and preparation method thereof |
-
2020
- 2020-09-22 CN CN202011003614.7A patent/CN112076776B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112076776A (en) | 2020-12-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108927198B (en) | Modified carbon nitride photocatalyst, preparation method thereof and method for synthesizing xylonic acid by photocatalytic oxidation of xylose | |
| CN112076776B (en) | Protonated carbon nitrides for selective photocatalytic oxidation of alcohols to esters and uses thereof | |
| CN111960948B (en) | Synthesis process of tetrabutylammonium bromide | |
| CN111889129B (en) | Preparation of ultrathin porous nano carbon nitride photocatalyst and application of ultrathin porous nano carbon nitride photocatalyst in synthesis of lactic acid by photocatalytic oxidation of fructose | |
| CN110194730B (en) | Application of DUT-67(Zr) in preparation of methyl phenyl sulfoxide through photocatalytic oxidation of methyl phenyl sulfide | |
| CA2198777C (en) | Photocatalyst, method for preparing the same, and production of hydrogen using the same | |
| CN111408392A (en) | Cobalt-nitrogen co-doped porous carbon material catalyst and preparation method and application thereof | |
| CN113527703B (en) | Metal carbon-based coordination polymer, preparation method and application thereof in synthesis of 2,5-furandimethanol | |
| CN109772326A (en) | A kind of catalyst and its preparation method and application synthesizing Fluorenone | |
| CN107286006B (en) | Method for preparing vanillone and acetosyringone by catalytic alcoholysis of lignin | |
| CN108530318B (en) | Method for synthesizing adiponitrile | |
| CN101450324A (en) | Polymer-bound tripe amino-acid schiff base metal copper complexes catalyst and synthesis method thereof | |
| CN109772419B (en) | Preparation method for constructing carbon nitride-based ultrathin nanosheet composite material in confined space | |
| CN110437189B (en) | Preparation method of 5-formyl-2-furancarboxylic acid | |
| CN108586202B (en) | Synthesis method of intermediate 4-phenylbutanol | |
| CN113908873B (en) | Method for selectively oxidizing glucose by photocatalysis of carbon nitride-based photocatalyst | |
| CN105111128A (en) | Method for preparing N-hydroxyphthalimide | |
| CN110270378B (en) | Porous polymer supported palladium catalyst CaPOP3@ Pd for triazine-based connection of calix [4] arene, and preparation method and application thereof | |
| CN108640829A (en) | A kind of method that aqueous catalysis Oxidation of Lactic prepares pyruvic acid | |
| CN115286506B (en) | Method for synthesizing matrithrin by one-step oxidation esterification with metal organic framework material as catalyst | |
| CN1958160A (en) | Cu-VSB 5 catalyst for hydroxylation of phenol, and preparation method | |
| CN115709073B (en) | Preparation method of tin-based catalyst and application of tin-based catalyst in catalyzing biomass sugar to prepare methyl lactate | |
| CN114768877B (en) | Cellulose-loaded Cu 2 O/TiO 2 Catalytic material and method for applying catalytic material to boron addition reaction of p-benzoquinone methide | |
| CN114289045B (en) | Hydrogenation catalyst and application thereof in preparing cyclopentanone or furfuryl alcohol by catalyzing hydrogenation of furfural | |
| CN115007173B (en) | CuInS 2 Preparation of quantum dot carbon aerogel photocatalyst and application of quantum dot carbon aerogel photocatalyst in synthesis of xylonic acid by photocatalytic oxidation of xylose |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |