CN114956118A - Method for reducing nitrogen into ammonia by visible light photocatalysis - Google Patents

Method for reducing nitrogen into ammonia by visible light photocatalysis Download PDF

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CN114956118A
CN114956118A CN202210363309.1A CN202210363309A CN114956118A CN 114956118 A CN114956118 A CN 114956118A CN 202210363309 A CN202210363309 A CN 202210363309A CN 114956118 A CN114956118 A CN 114956118A
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visible light
ammonia
solution
nitrogen
sacrificial agent
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郝策
李彦文
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Dalian University of Technology
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Dalian University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/60—Reduction reactions, e.g. hydrogenation
    • B01J2231/62—Reductions in general of inorganic substrates, e.g. formal hydrogenation, e.g. of N2
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
    • B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
    • B01J2531/025—Ligands with a porphyrin ring system or analogues thereof, e.g. phthalocyanines, corroles
    • 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
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/845—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
    • B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

The invention belongs to the technical field of photocatalysis, and provides a method for reducing nitrogen into ammonia by visible light photocatalysis, which comprises the following steps: the sulfonated cobalt phthalocyanine, the alkaline substance, the sacrificial agent and the water are stirred and mixed evenly, and the nitrogen is reduced into ammonia under the condition of a nitrogen source by illumination catalysis. The method avoids using a noble metal catalyst, has mild reaction conditions, low energy consumption, simple operation and high selectivity, adopts visible light catalysis, has the characteristics of no pollution, environmental friendliness and the like, and is a promising method.

Description

Method for reducing nitrogen into ammonia by visible light photocatalysis
Technical Field
The invention belongs to the technical field of energy materials and photocatalysis, and particularly relates to a method for fixing nitrogen by photocatalysis by adjusting reaction conditions by using sulfonated cobalt phthalocyanine as a photocatalyst.
Background
Nitrogen is an important element for synthesizing amino acids and nucleic acids, and although the atmosphere contains abundant nitrogen, it cannot be directly utilized because of its strong chemical triple bond, and it can be used only by converting it into ammonia or nitrogen oxide. At present, two main ways of fixing nitrogen in nature are available, one is lightning nitrogen fixation, and the other is microorganism nitrogen fixation, but with the improvement of science and technology, the natural nitrogen fixation way is not enough to meet the requirements of human beings, so artificial nitrogen fixation needs to be developed.
The photosensitive dye has special optical properties, and can better absorb visible light, absorb sunlight and then convert the sunlight into chemical energy. The dye has the following characteristics for excellent photosensitive dye: 1) the light-emitting diode has a wider response spectrum and a higher molar absorption coefficient in a visible light region; 2) the LUMO and HOMO of the dye molecule have higher oxidation-reduction potential; 3) the compound has larger steric hindrance, and the solubility of molecules is increased; 4) it has good light stability, thermal stability and chemical stability. For example, Liang F, Shi F, Fu Y, et al solar energy materials and solar cells,2010,94(10):1803-1808, of Changchun applied chemistry institute synthesize the phthalocyanine photosensitive dye ZnPc-TDA, which has strong absorption in the range of 400-600 nm, thereby enhancing the catalytic activity. Eu Seunghun et al [ Eu Seunghun, Katoh T, Umeyama T, et al Dalton Transactions,2008(40): 5476-.
Based on the analysis, the invention provides that sulfonated cobalt phthalocyanine is used as a catalyst, and photocatalytic nitrogen reduction is carried out by adjusting the pH of the solution and adding a sacrificial agent. We propose this approach with the following considerations: the sulfonated cobalt phthalocyanine has good light stability, thermal stability and chemical stability as a dye, has a relatively wide response spectrum and absorption intensity in a visible light region, and is an ideal photocatalyst.
Disclosure of Invention
The invention aims to provide a method for photocatalytic reduction of nitrogen into ammonia by using visible light.
The technical scheme of the invention is as follows:
a method for reducing nitrogen into ammonia by visible light photocatalysis is characterized by selecting sulfonated cobalt phthalocyanine as a photocatalyst, fully grinding the photocatalyst, uniformly mixing and stirring the ground photocatalyst, an alkaline substance, a sacrificial agent and water, and carrying out photocatalysis for 1-10 hours under the conditions of nitrogen atmosphere and visible light illumination at normal temperature and normal pressure to obtain ammonia;
wherein the concentration of the sacrificial agent in the solution is 0.1-3.0 mol.L -1 (ii) a The concentration of the catalyst in the solution is 100-150mg & L -1 (ii) a The pH of the solution is 7-14.
Further, the sacrificial agent is at least one of methanol, ethanol, sodium sulfite and isopropanol, and the concentration of the sacrificial agent in the solution is 1.4-1.6 mol.L -1 。
Further, the alkaline substance is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide and potassium carbonate.
Further, the concentration of the catalyst in the solution was 120-130 mg. L -1 。
Further, the alkaline substance is sodium hydroxide;
the sacrificial agent is methanol;
the pH value of the solution is 11-13;
the visible light source is a 300W xenon lamp provided with a 420nm filter, and the illumination time is 2-4 h.
The invention has the beneficial effects that:
the method selects the dye sulfonated cobalt phthalocyanine as the photocatalyst, successfully reduces nitrogen into ammonia by selecting proper pH value of solution, a sacrificial agent and illumination conditions, improves the yield of the product ammonia, has mild reaction conditions and low energy consumption, avoids using a noble metal catalyst, and greatly reduces the production cost. The dye sulfonated cobalt phthalocyanine is used as a photocatalyst and has a proper LUMO-HOMO orbital potential, so that the reaction can be smoothly carried out without adding a photosensitizer. Because the water molecules are difficult to be oxidized, the methanol is selected as a sacrificial agent to participate in the reaction, the methanol is oxidized into formaldehyde, and the reaction rate is greatly improved.
Drawings
FIG. 1 is the mass spectrum of the product analysis of the cobalt sulfonated phthalocyanine photocatalytic nitrogen reduction
Detailed Description
The following further describes a specific embodiment of the present invention with reference to the drawings and technical solutions.
Example 1
Grinding appropriate amount of sulfonated cobalt phthalocyanine solid powder, and adding into 80mL boiled ultrapure water to make catalyst concentration 125 mg.L -1 Adding methanol as sacrificial agent to make the concentration of methanol in the solution be 1.5 mol.L -1 Adjusting the pH value of the solution to 13 by adopting sodium hydroxide, connecting the solution to a nitrogen atmosphere, illuminating for 4 hours under a 300W xenon lamp with a 420nm filter, and detecting by adopting a Nashin reagent method. The yield of ammonia was 2855.7. mu. mol. L -1 ·g -1 ·h -1 。
Example 2
The pH of the solution was adjusted with sodium hydroxide, potassium hydroxide, sodium hydroxide and sodium carbonate, potassium hydroxide and potassium carbonate, respectively, as in example 1. When sodium hydroxide is used for adjusting the pH value of the solution, the yield of ammonia is 2855.7 mu mol.L -1 ·g -1 ·h -1 (ii) a When potassium hydroxide is used for adjusting the pH value of the solution, the yield of ammonia is 2467.6 mu mol.L -1 ·g -1 ·h -1 (ii) a When sodium hydroxide and sodium carbonate are adopted to adjust the pH value of the solution, the yield of ammonia is 2587.4 mu mol.L -1 ·g -1 ·h -1 (ii) a The pH value of the solution is adjusted by adopting potassium hydroxide and potassium carbonate, so that the yield of ammonia is 2314.2 mu mol.L -1 ·g -1 ·h -1 . Therefore, sodium hydroxide is adopted to adjust the pH value of the solution.
Experimental example 3
The pH values of the solutions were adjusted to 11, 12 and 13 with sodium hydroxide, respectively, and the procedure was otherwise the same as in example 1. When the pH of the solution was 11, the yield of ammonia was 2333.0. mu. mol. L -1 ·g -1 ·h -1 (ii) a When the solution had a pH of 12, the yield of ammonia was 2613.3. mu. mol. multidot.L -1 ·g -1 ·h -1 (ii) a When the solution pH was 13, the yield of ammonia was 2855.7. mu. mol. multidot.L -1 ·g -1 ·h -1 . Therefore, sodium hydroxide is used to adjust the pH value of the solution to 13.
Example 4
Respectively taking a proper amount of sulfonated cobalt phthalocyanine solid powder, grinding, adding into 80mL of boiled ultrapure water to ensure that the catalyst concentration is 120 mg.L -1 、125mg·L -1 、130mg·L -1 . The pH of the solution was adjusted with sodium hydroxide, otherwise as in example 1. When the concentration of the catalyst is 120 mg.L -1 The yield of ammonia was 2715.2. mu. mol. L -1 ·g -1 ·h -1 (ii) a When the concentration of the catalyst is 125 mg.L -1 The yield of ammonia was 2855.7. mu. mol. L -1 ·g -1 ·h -1 (ii) a When the concentration of the catalyst is 130 mg.L -1 The yield of ammonia was 2689.3. mu. mol. L -1 ·g -1 ·h -1 . Therefore, the optimum concentration of the catalyst is 125 mg.L -1 。
Example 5
The same procedure as in example 1 was repeated, except that methanol, ethanol, sodium sulfite and isopropanol were used as the sacrificial agents, respectively. When methanol was used as the sacrificial agent, the yield of ammonia was 2855.7. mu. mol. L -1 ·g -1 ·h -1 (ii) a The yield of ammonia was 1932.5. mu. mol. L when ethanol was used as the sacrificial agent -1 ·g -1 ·h -1 (ii) a When sodium sulfite was used as a sacrificial agent, the ammonia yield was 1238.2. mu. mol. L -1 ·g -1 ·h -1 (ii) a When isopropanol was used as a catalyst, the yield of ammonia was 1312.7. mu. mol. L -1 ·g -1 ·h -1 . Methanol was chosen as the sacrificial agent.
Example 6
The concentration of methanol in the solution was adjusted to 1.4 mol. L, respectively -1 、1.5mol·L -1 、1.6mol·L -1 Otherwise, the same procedure as in example 1 was repeated. When the concentration of methanol is 1.4 mol.L -1 The yield of ammonia was 2723.6. mu. mol. L -1 ·g -1 ·h -1 . When the concentration of methanol is 1.5 mol.L -1 The yield of ammonia was 2855.7. mu. mol. L -1 ·g -1 ·h -1 (ii) a When the concentration of methanol is 1.6 mol.L -1 The yield of ammonia was 2538.2. mu. mol. L -1 ·g -1 ·h -1 . Therefore, the optimal concentration of the methanol as the sacrificial agent is 1.5 mol.L -1 。
Example 7
The light source was selected from natural light and 300W xenon lamp with 420nm filter, and the other examples were the same as example 1. The yield of ammonia was 691.7. mu. mol. L when natural light was used as the light source -1 ·g -1 ·h -1 (ii) a When a 300W xenon lamp with a 420nm filter is used as a light source, the yield of ammonia is 2855.7 mu mol.L -1 ·g -1 ·h -1 . Therefore, the light source is a 300W xenon lamp with a 420nm filter.
The above embodiments are preferred or best mode embodiments of the present invention, and the above description is only for the purpose of facilitating understanding of the method of the present invention, and it should be noted that it is possible for those skilled in the art to make modifications and changes to the present invention without departing from the principle of the present invention, and those modifications and changes also fall into the protection scope of the present invention.

Claims (8)

1. A method for reducing nitrogen into ammonia by visible light photocatalysis is characterized in that sulfonated cobalt phthalocyanine is selected as a photocatalyst, the photocatalyst is fully ground, the ground photocatalyst, an alkaline substance, a sacrificial agent and water are uniformly mixed and stirred, and the mixture is subjected to photocatalysis for 1-10 hours under the conditions of nitrogen atmosphere and visible light illumination at normal temperature and normal pressure to obtain ammonia;
wherein the concentration of the sacrificial agent in the solution is 0.1-3.0 mol.L -1 (ii) a The concentration of the catalyst in the solution is 100-150 mg.L -1 (ii) a The pH of the solution is 7-14.
2. The method of claim 1, wherein the sacrificial agent is at least one of methanol, ethanol, sodium sulfite, and isopropanol, and the concentration of the sacrificial agent in the solution is 1.4-1.6 mol-L -1 。
3. The method of visible light photocatalytic nitrogen reduction to ammonia according to claim 1 or 2, characterized in that the basic substance is at least one of sodium hydroxide, sodium carbonate, potassium hydroxide, potassium carbonate.
4. The method for visible light photocatalytic nitrogen reduction to ammonia according to claim 1 or 2, characterized in that the catalyst concentration in the solution is 120-130 mg-L -1 。
5. The method as claimed in claim 3, wherein the concentration of the catalyst in the solution is 120-130 mg-L -1 。
6. The method of visible light photocatalytic nitrogen reduction to ammonia according to claim 1, 2 or 5,
the alkaline substance is sodium hydroxide;
the sacrificial agent is methanol;
the pH value of the solution is 11-13;
the visible light source is a 300W xenon lamp provided with a 420nm filter, and the illumination time is 2-4 h.
7. The method of claim 3, wherein the visible light catalyzes the reduction of nitrogen to ammonia,
the alkaline substance is sodium hydroxide;
the sacrificial agent is methanol;
the pH value of the solution is 11-13;
the visible light source is a 300W xenon lamp provided with a 420nm filter, and the illumination time is 2-4 h.
8. The method of claim 4, wherein the visible light is used to photocatalyze the reduction of nitrogen to ammonia,
the alkaline substance is sodium hydroxide;
the sacrificial agent is methanol;
the pH value of the solution is 11-13;
the visible light source is a 300W xenon lamp provided with a 420nm filter, and the illumination time is 2-4 h.
CN202210363309.1A 2022-04-08 2022-04-08 Method for reducing nitrogen into ammonia by visible light photocatalysis Pending CN114956118A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116375052A (en) * 2023-05-19 2023-07-04 大连理工大学 Homogeneous photocatalyst is prepared by mixing N 2 Reduction to NH 3 Is a method of (2)

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128621A (en) * 1976-10-28 1978-12-05 Uop Inc. Production of ammonia
CN101052762A (en) * 2004-08-30 2007-10-10 西巴特殊化学制品控股公司 Shading process
CN104785296A (en) * 2015-04-17 2015-07-22 中国石油大学(华东) Liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas mercaptan removal
CN105170192A (en) * 2015-10-26 2015-12-23 北京科技大学 Preparation method for sulfonated cobalt phthalocyanine sensitized titanium dioxide compound photocatalyst
CN105833913A (en) * 2016-04-13 2016-08-10 河海大学 Chemical modified titanium dioxide photocatalyst and preparation method thereof
CN107855130A (en) * 2017-11-23 2018-03-30 大连工业大学 A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method
CN109794294A (en) * 2019-02-11 2019-05-24 盐城师范学院 A kind of photochemical catalyst and its preparation method and application of sulfonated metal phthalocyanine@ZIF-8
CN111527851A (en) * 2020-05-13 2020-08-14 浙江大学 Photocatalytic foliar fertilization method
CN112916000A (en) * 2021-01-15 2021-06-08 兰州大学 Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof
CN113213508A (en) * 2021-04-27 2021-08-06 金华市浙工大创新联合研究院 Method for synthesizing ammonia through photocatalysis

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4128621A (en) * 1976-10-28 1978-12-05 Uop Inc. Production of ammonia
CN101052762A (en) * 2004-08-30 2007-10-10 西巴特殊化学制品控股公司 Shading process
CN104785296A (en) * 2015-04-17 2015-07-22 中国石油大学(华东) Liquid cobalt sulfonated phthalocyanine catalyst for liquefied petroleum gas mercaptan removal
CN105170192A (en) * 2015-10-26 2015-12-23 北京科技大学 Preparation method for sulfonated cobalt phthalocyanine sensitized titanium dioxide compound photocatalyst
CN105833913A (en) * 2016-04-13 2016-08-10 河海大学 Chemical modified titanium dioxide photocatalyst and preparation method thereof
CN107855130A (en) * 2017-11-23 2018-03-30 大连工业大学 A kind of solar energy fixed nitrogen photochemical catalyst and application thereof and preparation method
CN109794294A (en) * 2019-02-11 2019-05-24 盐城师范学院 A kind of photochemical catalyst and its preparation method and application of sulfonated metal phthalocyanine@ZIF-8
CN111527851A (en) * 2020-05-13 2020-08-14 浙江大学 Photocatalytic foliar fertilization method
CN112916000A (en) * 2021-01-15 2021-06-08 兰州大学 Photocatalytic material for reducing nitrogen to produce ammonia and preparation method and application thereof
CN113213508A (en) * 2021-04-27 2021-08-06 金华市浙工大创新联合研究院 Method for synthesizing ammonia through photocatalysis

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116375052A (en) * 2023-05-19 2023-07-04 大连理工大学 Homogeneous photocatalyst is prepared by mixing N 2 Reduction to NH 3 Is a method of (2)
CN116375052B (en) * 2023-05-19 2024-03-22 大连理工大学 Homogeneous photocatalyst is prepared by mixing N 2 Reduction to NH 3 Is a method of (2)

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Application publication date: 20220830