CN114558623B - Preparation method of Ru-loaded hydroxyl MOF photocatalyst and application of Ru-loaded hydroxyl MOF photocatalyst in nitrogen fixation ammonia synthesis - Google Patents
Preparation method of Ru-loaded hydroxyl MOF photocatalyst and application of Ru-loaded hydroxyl MOF photocatalyst in nitrogen fixation ammonia synthesis Download PDFInfo
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- CN114558623B CN114558623B CN202111501457.7A CN202111501457A CN114558623B CN 114558623 B CN114558623 B CN 114558623B CN 202111501457 A CN202111501457 A CN 202111501457A CN 114558623 B CN114558623 B CN 114558623B
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 28
- 125000002887 hydroxy group Chemical group [H]O* 0.000 title claims abstract description 26
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 20
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title abstract description 67
- 229910052757 nitrogen Inorganic materials 0.000 title abstract description 33
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Substances CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 238000001354 calcination Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 239000004570 mortar (masonry) Substances 0.000 claims abstract description 4
- 239000002244 precipitate Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 29
- 230000000694 effects Effects 0.000 abstract description 17
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 230000008859 change Effects 0.000 abstract description 6
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 3
- 239000011363 dried mixture Substances 0.000 abstract 2
- 238000000643 oven drying Methods 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 description 48
- 238000011068 loading method Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 12
- 239000011148 porous material Substances 0.000 description 9
- 239000011701 zinc Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 238000003917 TEM image Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 238000002189 fluorescence spectrum Methods 0.000 description 5
- 238000013507 mapping Methods 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000006798 recombination Effects 0.000 description 4
- 238000005215 recombination Methods 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical group [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- XYVDNBKDAAXMPG-UHFFFAOYSA-M decyl 2-(1-heptylazepan-1-ium-1-yl)acetate;hydroxide Chemical compound [OH-].CCCCCCCCCCOC(=O)C[N+]1(CCCCCCC)CCCCCC1 XYVDNBKDAAXMPG-UHFFFAOYSA-M 0.000 description 1
- UXGNZZKBCMGWAZ-UHFFFAOYSA-N dimethylformamide dmf Chemical compound CN(C)C=O.CN(C)C=O UXGNZZKBCMGWAZ-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000005283 ground state Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012073 inactive phase Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000002773 nucleotide Substances 0.000 description 1
- 125000003729 nucleotide group Chemical group 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
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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
- C01C1/026—Preparation of ammonia from inorganic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
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Abstract
The invention relates to the field of photocatalysis nitrogen fixation, and discloses a preparation method of Ru-loaded hydroxyl MOF photocatalyst and application thereof in nitrogen fixation ammonia synthesis, wherein the method comprises the steps of adding 2, 5-dihydroxyterephthalic acid, zn (NO) 3 ) 2 ·6H 2 O and RuCl 3 Dissolving in DMF solvent, magnetically stirring until the solid is completely dissolved, and adding deionized water to completely mix; dropwise adding triethylamine into the solution to form light yellow precipitate; centrifuging with a centrifuge, oven drying the obtained solid in a vacuum drying oven, grinding with a mortar, washing the ground powder with deionized water and ethanol respectively, and collecting the washed powderAnd (3) putting the dried mixture into a tube furnace after centrifugal drying, and calcining the dried mixture in a hydrogen atmosphere to obtain the Ru-loaded hydroxyl MOF photocatalyst. According to the invention, the metal Ru is loaded on the OH-MOF to enable the metal Ru to be dispersed to a great extent, the Ru stability is enhanced and is not easy to change, the utilization rate is improved, and the photocatalytic nitrogen fixation activity is improved.
Description
Technical Field
The invention relates to the technical field of photocatalysis nitrogen fixation, in particular to a preparation method of Ru-loaded hydroxyl MOF photocatalyst and application thereof in nitrogen fixation ammonia synthesis.
Background
Nitrogen is an essential element of biomolecules such as proteins, nucleotides and other biological compounds in plants and animals. Although nitrogen molecule (N) 2 ) Is the main component on earth (about 78% in the atmosphere), but has a bond energy of 940.95 kJ mol due to the highly stable covalent triple bond of nitrogen and nitrogen - 1 Therefore, it is not nutritionally available. Therefore, high pressure and high temperature (150-350 atm, 350-550 ℃) are industrially required to convert N 2 Conversion to useful nitrogen-containing compounds, e.g. NH 3 . The annual energy consumption by the Haber-Bosch (Haber-Bosch) process is 1-2% of the world. In addition, the Haber-Bosch method synthesizes NH 3 The hydrogen gas is generated by steam reforming of natural gas, which is accompanied by a large amount of CO 2 And (5) discharging. Under the background of shortage of fossil fuel and global climate change, a catalytic production method for NH under the condition of mild environment by utilizing nitrogen and rich hydrogen source on earth is explored 3 Is highly desirable.
In recent years, various sustainable N has been developed by means of biological nitrogen fixation enzyme, photocatalysis, electrocatalysis and the like 2 -NH 3 The route is fixed. As a method for synthesizing NH under mild environmental reaction conditions 3 Is to reduce N by photocatalysis 2 Reduction to NH 3 There is particular interest in the process because the process uses water as a hydrogen source and solar energy as an energy source, and the reaction conditions are mild and pollution-free. Thus, the development of high activity photocatalysts for NH production 3 Is desirable but still challenging. The low yield is a major problem limiting the practical application of the photocatalytic nitrogen fixation to ammonia, and compared with the electrocatalytic process, the photocatalytic nitrogen fixation has the advantages that the energy source is solar energy, and no extra electric energy is needed for reaction. But the yield is far lower than that of electrocatalytic nitrogen fixation to ammonia. The main reasons for low photocatalytic nitrogen fixation yields are the following: 1. the photo-generated carriers are seriously compounded, so that the concentrations of photo-generated electrons and photo-generated holes which can participate in the reaction are low; 2. the low utilization of visible light results in low photocatalytic activity. Visible light accounts for about 50% of sunlight, and when a wide-bandgap catalyst reacts under illumination, the wide-bandgap catalyst has strong oxidation-reduction capability, but only responds to ultraviolet light, and the ultraviolet light energy accounts for less than 10% of total light, so that the catalytic activity is low; 3. the photocatalytic nitrogen fixation is mainly used for generating ammonia by utilizing photo-generated electrons to participate in reduction reaction, the oxidation reaction of photo-generated holes is slower, and the consumption speed of the photo-generated holes drags down the reduction reaction speed of the photo-generated electrons, so that the photocatalytic activity is lower.
In addition to the several reasons mentioned above, the factors affecting the activity of photocatalytic nitrogen fixation are also affected by the hydrogen source compared to several other photocatalysts. It is known that the hydrogen source for synthesizing ammonia by photocatalytic nitrogen fixation is derived from water, which generates active hydrogen and active hydrogen-oxygen under the catalysis of a photocatalyst, and the active hydrogen is combined with nitrogen in subsequent reactions to generate ammonia. But compared with the reaction with nitrogen to produce ammonia (NH) 3 ) Active hydrogen is more likely to combine with itself to generate hydrogen (H) 2 ) This severely reduces the concentration of active hydrogen and thus affects the yield of synthetic ammonia. How to inhibit the generation of hydrogen and how to carry out the reaction like the synthesis of ammonia is one of the main problems of the photocatalytic nitrogen fixation to generate ammonia, and has been widely studied in recent years. It has recently been reported that metal Ru can inhibit the generation of hydrogen in photocatalytic nitrogen fixation, thereby causing the reactionMore in the direction of the synthesis ammonia. Ru is a rare metal, and is one of the problems of high price, and how to improve the utilization rate and make Ru be dispersed and utilized effectively. Ru is used as one of noble metals, and is changed under the action of photocatalysis to cause instability, so that the recycling rate is low.
Disclosure of Invention
The invention aims to: aiming at the problems existing in the prior art, the invention provides a preparation method of a Ru-loaded hydroxyl MOF photocatalyst and application thereof in nitrogen fixation ammonia synthesis, and as the OH-MOFOH-MOF has a pore structure and a larger specific surface area than that of inorganic matters, the metal Ru is loaded on the OH-MOF to ensure that the metal Ru is dispersed to a great extent, thereby improving the utilization rate, the Ru-loaded OH-MOF can effectively improve the photocatalytic nitrogen fixation activity, and the combination with the OH-MOF can ensure that the stability of the metal Ru is enhanced and is not easy to change.
The technical scheme is as follows: the invention provides a preparation method of a Ru-loaded hydroxyl MOF photocatalyst, which comprises the following steps: s1: 2,5 dihydroxyterephthalic acid, zn (NO) 3 ) 2 ·6H 2 O and RuCl 3 Dissolving in DMF solvent, magnetically stirring until the solid is completely dissolved, and adding deionized water until the solid is completely mixed to obtain a mixed solution; s2: dropwise adding triethylamine into the mixed solution to form light yellow precipitate; centrifuging by a centrifuge, putting the obtained solid into a vacuum drying oven for drying, grinding by a mortar after drying, respectively washing the powder obtained after grinding by deionized water and ethanol, and centrifuging and drying the washed powder; s3: and (3) placing the dried powder into a tube furnace, and calcining under the hydrogen atmosphere to obtain the Ru-loaded hydroxyl MOF photocatalyst.
Preferably, in S1, the 2,5 dihydroxyterephthalic acid, zn (NO 3 ) 2 ·6H 2 O and RuCl 3 The mass ratio of the components is 0.1:0.952:0.0066 to 0.0198.
Preferably, in S1, the volume ratio of deionized water to DMF solvent is 1:20.
preferably, the volume ratio of triethylamine in S2 to deionized water and DMF solvent in S1 is 1:20:10. preferably, in S2, the drying temperature is 120-140 ℃ when the obtained solid is put into a vacuum drying oven for drying.
Preferably, in S3, the conditions for calcination under a hydrogen atmosphere are as follows: heating to 190-220 ℃ at a speed of 2-3 ℃/min, and calcining for 1.5-2.5 hours.
The invention also provides application of the Ru-loaded hydroxyl MOF photocatalyst prepared by the method in nitrogen fixation synthesis of ammonia.
The beneficial effects are that: because the OH-MOF has a pore structure and the specific surface area is larger than that of inorganic matters, the metal Ru is carried on the OH-MOF to enable the metal Ru to be dispersed to a great extent, so that the utilization rate is improved, the photocatalytic nitrogen fixation activity can be effectively improved by carrying the OH-MOF with Ru, and the stability of the metal Ru is enhanced and is not easy to change due to the combination of the Ru and the OH-MOF, because the OH-MOF has a good fixing effect on Ru due to unsaturated coordination sites and pore channels of the metal Ru.
The application successfully loads Ru with various contents on the OH-MOF template by a thermal reduction method, and greatly improves the photocatalytic nitrogen fixation activity of the OH-MOF. Experimental analysis shows that the OH-MOF catalyst loaded with 2% Ru has excellent performance in the characteristics of fluorescence, photocurrent, alternating current impedance and the like. Besides the surface load, ru is also largely introduced into the pore canal of the OH-MOF through the UV-vis absorption.
Drawings
FIG. 1 shows the chromogenic UV absorbance (a) and standard curve (b) of indophenol blue at different standard concentrations;
FIG. 2 is an XRD pattern for 1% Ru, 2% Ru, 3% Ru (OH-MOF) and OH-MOF;
in FIG. 3, (a) is a STEM diagram of an OH-MOF sample; (b) is a TEM image of an OH-MOF sample;
in FIG. 4, (a) is a STEM diagram of a 1% Ru (OH-MOF) sample; (b) TEM images of 1% Ru (OH-MOF) samples;
in FIG. 5, (a) is a STEM diagram of a 2% Ru (OH-MOF) sample; (b) TEM images of 2% Ru (OH-MOF) samples;
in FIG. 6, (a) is a STEM diagram of a 3% Ru (OH-MOF) sample; (b) TEM images of 3% Ru (OH-MOF) samples;
in FIG. 7, (a) is a TEM image of 2% Ru (OH-MOF); (b) a Zn element Mapping graph; (c) a Ru element Mapping graph;
FIG. 8 is a graph of the activities of 1% Ru, 2% Ru, 3% Ru (OH-MOF) and OH-MOF;
FIG. 9 shows fluorescence spectra of 1% Ru, 2% Ru, 3% Ru (OH-MOF);
FIG. 10 is an OH-MOF AC impedance plot of 1% Ru, 2% Ru, 3% Ru (OH-MOF);
FIG. 11 is a photoelectrographic plot of 1% Ru, 2% Ru, 3% Ru (OH-MOF) and OH-MOF;
FIG. 12 is a UV-vis absorption diagram of 1% Ru, 2% Ru, 3% Ru (OH-MOF) and OH-MOF.
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Experimental medicine and main instrument
1. Experimental medicine and specification
N, N dimethylformamide DMF analytically pure Conrader reagent
Zinc nitrate hexahydrate Zn (NO) 3 ) 2 ·6H 2 O analytically pure Aba Ding Shiji
Triethylamine analytically pure Conrader reagent
2, 5-dihydroxyterephthalic acid 2,5-BDC analytically pure Michael reagent
Ethanol C 2 H 5 Chemical industry of OH analysis pure Tianjin Jiang Tian
Chromatographic pure water Concore reagent
RuCl of ruthenium trichloride 3 Analytically pure enoKai reagent
2. Main instrument
Beijing Zhongzhui zhu jinyuan (teaching gold source) glass reactor
Electronic balance QUINTIX125D-1CN Sidolisco instrument (Beijing)
Beijing Zhongzhui zhu jinyuan (teaching gold source) glass reactor
Magnetic stirrer RCT basic package IKA group Germany
Muffle furnace KSW-512 Tianjin middle ring
Centrifuge TG16-WS/TG16WS Xiangtan Hunan instrument
Electric heating constant temperature blast drying box DH-101 Tianjin middle ring
X-ray powder diffractometer MiniFlex 600 Japan Physics Co
Transmission Electron microscope JEM-2800 JEOL Japanese Electron Co
ESCALAB 250Xi Thermo Scientific of X-ray photoelectron spectroscopy analyzer
Ultraviolet visible spectrophotometer U-4100 Hitachi
Fluorescence spectrometer FLS920 Edinburgh Instruments
Embodiment 1:
the embodiment provides a preparation method of a Ru-loaded hydroxyl MOF (OH-MOF) photocatalyst, which comprises the following specific steps:
0.1 g (0.52 mmol) 2, 5-dihydroxyterephthalic acid (2, 5-BDC), 0.952 g (1.52 mmol) Zn (NO) 3 ) 2 ·6H 2 O and 6.6mg (0.03 mmol) RuCl 3 Dissolved in 200 ml DMF solvent and magnetically stirred until the solid was completely dissolved. Then 10 ml deionized water was added dropwise to the solution until completely mixed to obtain a mixed solution. Subsequently, 1 ml triethylamine was added dropwise to the mixed solution, forming a pale yellow precipitate. And (3) centrifuging by a centrifuge, putting the obtained solid into a vacuum drying oven, drying at 130 ℃, grinding by using a mortar after drying, and continuously washing the powder obtained after grinding with deionized water and ethanol for 3 times respectively. And (5) continuously centrifuging and drying the washed powder. Finally, the powder is put into a tube furnace, and is heated to 200 ℃ at a speed of 2.5 ℃/min under the hydrogen atmosphere, and then calcined for 2 hours to reduce trivalent ruthenium, so as to obtain the Ru-loaded hydroxyl MOF photocatalyst, which is marked as 1% Ru (OH-MOF), wherein the Ru accounts for 1% of the hydroxyl MOF by mass.
Embodiment 2:
the present embodiment is substantially the same as embodiment 1, and is mainly different from embodiment 0.1. 0.1 g #0.52 mmol) 2,5 dihydroxyterephthalic acid (2, 5-BDC), 0.952 g (1.52 mmol) Zn (NO) 3 ) 2 ·6H 2 O and 13.2 mg (0.06 mmol) RuCl 3 Dissolved in 200 ml DMF solvent.
The final Ru-loaded hydroxyl MOF photocatalyst is recorded as 2% Ru (OH-MOF), which means that the Ru accounts for 2% of the hydroxyl MOF in mass fraction.
Otherwise, this embodiment is identical to embodiment 1, and a description thereof will be omitted.
Embodiment 3:
this embodiment is substantially the same as embodiment 1, and is mainly different from 0.1. 0.1 g (0.52 mmol) of 2, 5-dihydroxyterephthalic acid (2, 5-BDC) and 0.952 g (1.52 mmol) of Zn (NO) 3 ) 2 ·6H 2 O and 19.8 mg (0.09 mmol) RuCl 3 Dissolved in 200 ml DMF solvent.
The finally obtained Ru-loaded hydroxyl MOF photocatalyst is recorded as 3% Ru (OH-MOF), which means that the Ru accounts for 3% of the hydroxyl MOF in mass fraction.
Otherwise, this embodiment is identical to embodiment 1, and a description thereof will be omitted.
Characterization of the samples
At a scanning rate of 10 DEG min -1 Powder x-ray diffraction (XRD) patterns in the range of 3 ° -80 ° were recorded on Rigaku MiniFlex 600 using cuka radiation (λ= 0.154178 nm) at 298K. Electrochemical data testing was performed at the CHI760E electrochemical workstation. High Resolution TEM (HRTEM) images were detected using a JEM-2800 microscope. The samples were subjected to UV-visible spectrometry using a TU-1950 PERSEE spectrophotometer. Steady state fluorescence spectra were measured with Hitachi F-7000.
Photocatalytic reaction
The photocatalytic nitrogen fixation reaction was carried out in a medium-teaching Jin Yuanguang catalytic reactor (CEL-APR 100H). 10 mg catalyst was added to 50 ml H 2 Ultrasonic treatment is carried out in O solution for 15 min, then the solution is transferred into a photocatalysis reactor, nitrogen is introduced for 30 min to remove air, and finally the reactor is sealed. The reactor was operated with stirring at normal pressure by circulating condensed water to control the reaction temperature to 25 ℃. The light source used was a 300W Xe lamp (CEL-HXF 300),the xenon lamp was about 15 a cm a from the photocatalytic reactor and, when visible light catalysis was performed, filtering was performed using a 400 nm filter. Under illumination, 1 ml solution is taken every half hour and developed by indophenol blue development method, and NH is detected by ultraviolet visible spectrophotometer 4 + The content is as follows.
Standard curve
Vacuum drying 0.3142 g with 105 deg.C for more than 2 hr to obtain ammonium chloride (NH) 4 Cl), dissolved with a certain amount of water, added into a 100 ml volumetric flask, and then diluted with water until the scale mark is reached. This solution 1 ml contains 1 mg of ammonia and is diluted with water to a standard solution of different concentrations of ammonia when used. The standard solutions of ammonia with different concentrations were developed by indophenol blue development, and after 60 minutes development, the absorbance was measured by uv-vis spectrophotometer (fig. 1 a). With NH 3 The content is on the abscissa and the absorbance at 655 nm is on the ordinate to give the standard curve formula y=0.4045x+0.0228 (fig. 1 b).
Results and discussion
XRD spectrum
The crystal structure and composition of several catalyst samples prepared were characterized by XRD. FIG. 2 shows XRD patterns of 1% Ru, 2% Ru, 3% Ru (OH-MOF), respectively. It was found that OH-MOF was successfully synthesized, with two major peaks of OH-MOF at 6.7℃and 11.7 ℃. It was found that the peak position was not changed substantially after the Ru loading, but the peak intensity was different. At the same time we can find that after loading, the three peak intensities at 31.5 °, 34.4 °, 36.2 ° increase significantly. This is due to diffraction peaks of the zinc-oxygen structure formed by the coordination of oxygen in the ligand with metallic zinc.
STEM and TEM images
The morphology of the catalyst was characterized by STEM and TEM, from which we can clearly see that the morphology of the OH-MOF is small particles (fig. 3).
After loading 1% Ru, we can clearly see from the morphology that the morphology of the OH-MOF has changed to some extent (FIG. 4). The morphology of the OH-MOF is changed from small particles to a morphology of a rod-like and particle co-mixture formed by gradually forming the rod-like particles.
After loading 2% Ru (fig. 5), we can clearly see from the morphology that the morphology of the OH-MOF is similar to that before no Ru loading, all in small particles.
After loading with 3% Ru, we can find that the morphology of OH-MOF is different from before again (fig. 6), small particles with very small size, and no regular morphology is formed. By comparing the morphologies of the OH-MOF with different Ru loadings, the loading Ru has a larger influence on the morphology of the MOF, and the Ru loadings with different concentrations can generate certain changes on the OH-MOF.
TEM、Mapping
Since the central metal of the OH-MOF is Zn, the position of the MOF is characterized by the metallic zinc in Mapping. It can be seen from the Mapping graph of Zn and Ru elements at 2% Ru loading (FIG. 7) that the Ru distribution is relatively uniform, mainly due to the topology formed by the metallic nonmetallic building blocks and the bridging ligands that the MOF has.
Activity patterns
As can be seen from FIG. 8, the pure OH-MOF has a certain activity, and the catalyst activity is improved to a certain extent after the Ru is loaded in a certain content. Whereas the OH-MOF activity enhancement for 1% Ru and 2% Ru was very high, approximately 2.3 times that of 3% Ru (OH-MOF). From fig. 8, it can be seen that when the Ru loading reaches 3%, there is a large decrease in activity. This is confirmed by XPS to generate more inactive phase RuO 2 That is, when the concentration of the loaded Ru reaches a certain level, the active phase Ru is affected 0 The amount of the catalyst produced, and when the loading concentration is too high, also affects the contact of the catalyst with the reactant, thereby affecting the improvement of the activity.
Fluorescence spectrum
FIG. 9 shows fluorescence spectra of 1% Ru, 2% Ru, 3% Ru (OH-MOF). Fluorescence spectrum is the light emitted by a semiconductor when illuminated with light, and when a photogenerated electron returns from an excited state to a ground state. The side surface reflects the recombination rate of the photo-generated carriers to a certain extent, so that the photo-generated carriers have a certain relation with the photo-catalytic activity. As can be seen from the graph, the fluorescence intensity of 2% Ru (OH-MOF) was the lowest, which corresponds to the highest nitrogen fixation activity of 2% Ru (OH-MOF). Meanwhile, ru loading can effectively inhibit photon-generated carrier recombination, so that photocatalytic activity is improved.
Ac impedance diagram
The alternating current impedance reflects the charge transfer condition of the surface of the semiconductor material to a certain extent, the rapid transfer of charges is favorable for reaction, and the slower transfer of charges can lead to the recombination of electrons and holes. The smaller the alternating current impedance radius, the smaller the resistance, the faster the carrier transfer, the easier the catalytic reaction proceeds and thus the higher the catalytic activity. It can be seen from FIG. 10 that 1% Ru (OH-MOF) and 2% Ru (OH-MOF) have the smallest radii, which also corresponds well to photocatalytic nitrogen fixation activity.
Photoelectric diagram
Fig. 11 shows the photo-current graphs of different catalysts, and photo-current analysis is an effective method for researching the carrier separation and migration behavior of the photo-catalyst, and the photo-generated carrier capacity of the photo-catalyst is judged by detecting the current magnitude in the condition of no light irradiation. It can be seen that photocurrent of 2% ru (OH-MOF) is greatest. It can be seen from fig. 11 that the order of magnitude of the photocurrent corresponds to the order of photocatalytic nitrogen fixation activity. The reason is that the photo-current is only one of conditions affecting the photo-catalytic nitrogen fixation, and the photo-catalytic activity cannot be well demonstrated under the condition of large photo-current, and the photo-catalytic activity means that carriers migrate to the surface of the catalyst to be effectively captured by a reaction substrate, so that oxidation-reduction reaction occurs. Photocurrents are large only to indicate that bulk recombination is not severe, but do not indicate that carriers at the surface are effectively involved in the reaction.
UV-vis absorption diagram
It can be seen from FIG. 12 that there is some change in the UV-vis absorption of the OH-MOF after loading with Ru. The intrinsic absorption edge of the material is obviously shifted, so that the forbidden band width is changed. This suggests that Ru is not only supported on the surface of the OH-MOF, but also to some extent into the pores of the OH-MOF. The Ru in the pore canal can interact with the MOF to a certain extent, so that the valence state of the Ru is influenced. Meanwhile, the metal can have certain influence on the structure and the morphology of the metal after entering the pore canal, so that the light absorption can also have certain change. And a part of Ru ions form hybridization before reduction, and Ru is formed on the basis of the hybridization 0 Reducing clusters of (2). If only at the surface of the catalyst, its UV-vis absorption will only exhibit shoulder-like absorption changes, without the overall movement of the intrinsic absorption edge. This indicates that Ru has entered the bulk phase of the MOF material. Since the MOF is a porous material with holes, ru is likely to enter into the pores of the OH-MOF and exist stably.
The foregoing embodiments are merely illustrative of the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement the same, not to limit the scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (7)
1. The preparation method of the Ru-loaded hydroxyl MOF photocatalyst is characterized by comprising the following steps of:
s1: 2,5 dihydroxyterephthalic acid, zn (NO) 3 ) 2 ·6H 2 O and RuCl 3 Dissolving in DMF solvent, magnetically stirring until the solid is completely dissolved, and adding deionized water until the solid is completely mixed to obtain a mixed solution;
s2: dropwise adding triethylamine into the mixed solution to form light yellow precipitate; centrifuging by a centrifuge, putting the obtained solid into a vacuum drying oven for drying, grinding by a mortar after drying, respectively washing the powder obtained after grinding by deionized water and ethanol, and centrifuging and drying the washed powder;
s3: and (3) placing the dried powder into a tube furnace, and calcining under the hydrogen atmosphere to obtain the Ru-loaded hydroxyl MOF photocatalyst.
2. The method for preparing a Ru-supported hydroxyl MOF photocatalyst according to claim 1, wherein in S1, the 2,5 dihydroxyterephthalic acid, zn (NO 3 ) 2 ·6H 2 O and RuCl 3 The mass ratio of the components is 0.1:0.952:0.0066 to 0.0198.
3. The method for preparing a Ru-loaded hydroxyl MOF photocatalyst according to claim 1, wherein in S1, the volume ratio of deionized water to DMF solvent is 1:20.
4. the method for preparing the Ru-supported hydroxyl MOF photocatalyst according to claim 1, wherein the volume ratio of triethylamine in S2 to deionized water and DMF solvent in S1 is 1:10:200.
5. the method for preparing a Ru-loaded hydroxyl MOF photocatalyst according to claim 1, wherein in S2, the drying temperature when the obtained solid is dried in a vacuum drying oven is 120-140 ℃.
6. The method for producing a Ru-supported hydroxyl MOF photocatalyst according to any one of claims 1 to 5, wherein in S3, the conditions for calcination under a hydrogen atmosphere are as follows:
heating to 190-220 ℃ at a speed of 2-3 ℃/min, and calcining for 1.5-2.5 hours.
7. Use of a Ru-loaded hydroxyl MOF photocatalyst prepared by the method of any one of claims 1 to 6 in nitrogen-fixing synthesis of ammonia.
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