CN112457348A - Preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate - Google Patents
Preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate Download PDFInfo
- Publication number
- CN112457348A CN112457348A CN202011385819.6A CN202011385819A CN112457348A CN 112457348 A CN112457348 A CN 112457348A CN 202011385819 A CN202011385819 A CN 202011385819A CN 112457348 A CN112457348 A CN 112457348A
- Authority
- CN
- China
- Prior art keywords
- polyacid
- hybrid material
- organic hybrid
- metal organic
- silicotungstate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 93
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000001257 hydrogen Substances 0.000 claims abstract description 33
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 33
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000011572 manganese Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 claims abstract description 27
- UVERQPQFEHVFEB-UHFFFAOYSA-N 2-(1h-1,2,4-triazol-5-yl)pyrazine Chemical compound N1C=NC(C=2N=CC=NC=2)=N1 UVERQPQFEHVFEB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000013110 organic ligand Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 15
- 229910020628 SiW12O40 Inorganic materials 0.000 claims abstract description 10
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims abstract description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims abstract description 8
- 239000011565 manganese chloride Substances 0.000 claims abstract description 8
- 229940099607 manganese chloride Drugs 0.000 claims abstract description 8
- 235000002867 manganese chloride Nutrition 0.000 claims abstract description 8
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000013078 crystal Substances 0.000 claims description 18
- 238000000354 decomposition reaction Methods 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 17
- 230000000694 effects Effects 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 150000002696 manganese Chemical class 0.000 claims description 8
- 239000004065 semiconductor Substances 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 206010034972 Photosensitivity reaction Diseases 0.000 claims description 3
- 230000009286 beneficial effect Effects 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000036211 photosensitivity Effects 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 230000002195 synergetic effect Effects 0.000 claims description 2
- 238000006303 photolysis reaction Methods 0.000 claims 1
- 230000015843 photosynthesis, light reaction Effects 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 238000013461 design Methods 0.000 abstract description 2
- 238000006557 surface reaction Methods 0.000 abstract 1
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 18
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000002178 crystalline material Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000001144 powder X-ray diffraction data Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F13/00—Compounds containing elements of Groups 7 or 17 of the Periodic Table
- C07F13/005—Compounds without a metal-carbon linkage
-
- 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
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- 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
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses preparation and photocatalytic application of a polyacid-based manganese metal organic hybrid material constructed by silicotungstate, and relates to a polyacid-based manganese metal organic hybrid material constructed by silicotungstic acid. The invention aims to solve the problems that the photocatalytic hydrogen production material synthesized by the prior art has a wide forbidden band width, is easy to recombine photogenerated electron holes, is difficult to reduce surface reaction of protons, and the like, so that the conventional photocatalytic hydrogen production material does not produce hydrogen or has low hydrogen production quantity. The patent designs and develops a chemical formula (H) of a polyacid-based manganese metal organic hybrid material constructed by silicotungstate2SiW12O40)[Mn(pzta)3]2·4H2And O. Combination of Chinese herbsThe method comprises the following steps: silicotungstic acid, manganese chloride and organic ligand 5- (2-pyrazinyl) -1,2, 4-triazole are dissolved in deionized water, the pH is adjusted to 2.0, and the reaction is carried out for 3 days at the temperature of 160 ℃. The invention can obtain a polyacid-based manganese metal organic hybrid material constructed by silicotungstate.
Description
Technical Field
The invention relates to a polyacid-based manganese metal organic hybrid material constructed by silicotungstate.
Background
Facing the dual challenges of environment and energy, the key problem today is to find and utilize new clean, safe, renewable energy sources. However, natural solar energy is ubiquitous, is a renewable energy source, and is also an environmentally friendly and green clean energy source. Photocatalysis, which can convert solar energy into hydrogen and oxygen energy or high value-added chemical products, is receiving increasing attention from chemists and material scientists. The design of the photocatalyst is a core problem for realizing high-efficiency photocatalytic conversion of solar energy.
Polyoxometallates (POMs) are a class of inorganic functional materials with excellent physicochemical properties, including adjustable acidity, redox properties, oxidation resistance, thermal stability and good photoelectric properties, and become important inorganic building elements for constructing novel functional crystalline materials. The metal organic complex as a novel material is easy to separate, has less leaching problem, can be repeatedly used, reduces waste, and is green and clean. The metal organic complex has high specific surface area, high stability and ordered arrangement to obtain pores, so that the functional POMs can be combined with a template unit and a metal organic complex material to construct a polyacid-based metal-organic hybrid material. The polyacid-based metal-organic hybrid material combines the excellent performances of polyacid and metal-organic complex, the combination of the polyacid and the metal-organic complex is beneficial to the stability of the structure and the diversity of functions, not only can the respective advantages be fully exerted, but also the respective defects are overcome, and the functional combination of the polyacid and the metal-organic complex is realized. From the aspect of properties, the crystalline material not only has the excellent performance of polyacid, but also reflects the excellent properties of metal organic complexes, so that the polyacid-based metal-organic hybrid functional material has better photocatalytic application prospect.
Disclosure of Invention
The invention aims to solve the problems of high difficulty in synthesizing the polyacid-based manganese metal organic hybrid material and poor catalytic activity of the conventional polyacid serving as a photocatalyst for decomposing water to produce hydrogen, and provides a preparation method of the polyacid-based manganese metal organic hybrid material constructed by silicotungstate.
The chemical formula of the polyacid-based manganese metal organic hybrid material constructed by silicotungstate is (H)2SiW12O40)[Mn(pzta)3]2·4H2O, wherein pzta is 5- (2-pyrazinyl) -1,2, 4-triazole; the crystal system is monoclinic; space group is C2/C; unit cell parameters α -90 ° (5), β -107.037 ° (5), γ -90 ° (5),
z＝4。
a preparation method of polyacid-based manganese metal organic hybrid material constructed by silicotungstate is characterized in that the preparation method of polyacid-based manganese metal organic hybrid material with photocatalysis water decomposition hydrogen preparation effect is completed according to the following steps:
firstly, preparing a reaction solution with the pH value of 2.0, namely dissolving silicotungstic acid, manganese chloride and a 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand into deionized water to obtain the reaction solution; adjusting the pH value of the reaction solution to 2.0 to obtain a reaction solution with the pH value of 2.0;
the molar ratio of the silicotungstic acid to the metal manganese salt in the step one is 0.1 (0.2-1);
the molar ratio of the silicotungstic acid to the 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand in the step one is 0.1 (0.2-0.5);
the volume ratio of the silicotungstic acid substance in the step one to the distilled water is 0.1mmol (20 ml-35 ml);
secondly, adding the reaction solution with the pH value of 2.0 into a polytetrafluoroethylene reaction kettle, reacting for 3 days at 160 ℃, cooling to room temperature to obtain orange-yellow strip crystals, namely the polyacid-based manganese metal organic hybrid material;
the chemical formula of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate in the second step is (H)2SiW12O40)[Mn(pzta)3]2·4H2O, wherein pzta is 5- (2-pyrazinyl) -1,2, 4-triazole; the crystal system is monoclinic; space group is C2/C; unit cell parameters α -90 ° (5), β -107.037 ° (5), γ -90 ° (5),
z＝4。
a polyacid-based manganese metal organic hybrid material constructed by silicotungstate is used as a photocatalyst, 10% triethylamine is used as a sacrificial agent, and the proportion of acetone to water is 2: the solution 1 is used as a solvent to carry out photocatalytic decomposition on water and water to produce hydrogen, and has excellent catalytic efficiency.
Compared with the prior art, the invention has the following characteristics:
the invention adopts a simple one-step hydrothermal synthesis method, and successfully prepares the polyacid-based manganese metal organic hybrid material constructed by silicotungstate by using a 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand, manganese chloride and silicotungstic acid for the first time; the single crystal X-ray diffraction result shows that the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate not only has silicotungstic acid with good photosensitivity and strong reducing manganese metal atoms, but also has an ideal semiconductor structure formed by Keggin type polyacid silicotungstic acid and metal organic complexes, and the unique structure ensures that the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate has excellent photocatalytic water decomposition hydrogen production performance, and the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate can have high-efficiency and stable catalytic activity due to the fact that an active component polyacid inorganic unit structure is in a more stable bonding mode and a spatial arrangement mode.
At 0.25mol/L NaSO4In solution, it was electrochemically tested using an electrochemical workstation using impedance-potential (mott schottky test). To illustrate the inventionThe conduction band of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate is less than zero, so that the effect of photocatalytic water decomposition for hydrogen production is achieved. The catalytic performance of the material is mainly benefited by a special semiconductor structure, and the material is different from most of the traditional polyacid-based metal organic framework crystal materials.
The invention can obtain a polyacid-based manganese metal organic hybrid material constructed by silicotungstate.
Drawings
Fig. 1 is a schematic structural diagram of a polyacid-based manganese metal-organic hybrid material constructed by silicotungstate prepared in the first embodiment, where 1 in fig. 1 is silicon, 2 is oxygen, 3 is tungsten, 4 is manganese, 5 is carbon, 6 is nitrogen, 7 is water, and 8 is hydrogen;
FIG. 2 is a schematic diagram of a process for forming a polyacid-based manganese metal-organic hybrid material structure constructed by silicotungstate prepared in the first embodiment;
FIG. 3 is an infrared spectrum of a polyacid-based manganese metal organic hybrid material constructed by silicotungstate prepared in the first embodiment;
FIG. 4 is a PXRD pattern of a polyacid-based manganese metal-organic hybrid material constructed from silicotungstates prepared in the first example;
FIG. 5 is a Mott Schottky electrochemical performance test of the polyacid-based manganese metal-organic hybrid material constructed by silicotungstate prepared in the first embodiment;
FIG. 6 is a graph of hydrogen production rate of a polyacid-based manganese metal-organic hybrid material constructed by silicotungstate prepared in example one under 10% triethylamine as a sacrificial reagent for 6 hours.
Detailed Description
The process parameters and process routes of the present invention are not limited to the specific embodiments listed below, which are illustrative only and are not limiting of the process parameters and process routes described in the examples of the present invention. It should be understood by those skilled in the art that the present invention can be modified or substituted with equivalents in practical applications to achieve the same technical effects. As long as the application requirements are met, the invention is within the protection scope.
The chemical formula of the polyacid-based manganese metal organic hybrid material with the effect of photocatalytic decomposition of water to prepare hydrogen is (H)2SiW12O40)[Mn(pzta)3]2·4H2O, wherein pzta is 5- (2-pyrazinyl) -1,2, 4-triazole; the crystal system is monoclinic; space group is C2/C; unit cell parameters α -90 ° (5), β -107.336 ° (5), γ -90 ° (5),
z＝4。
(H) according to the present embodiment2SiW12O40)[Mn(pzta)3]2·4H2In O, the valence of Mn is +3 and +2, and the coordination mode is 6 coordination.
Compared with the prior art, the implementation mode has the following characteristics:
the invention adopts a simple one-step hydrothermal synthesis method, successfully prepares a polyacid-based manganese metal organic hybrid material constructed by silicotungstate by using a 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand, manganese chloride and silicotungstic acid for the first time; the single crystal X-ray diffraction result shows that the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate, prepared by the invention, contains silicotungstate with good photosensitivity and manganese atoms with reducibility, the semiconductor structure formed by polyacid and metal organic complex in the hybrid material has a narrow forbidden band width and a conduction band smaller than zero, and has a good effect of photocatalytic decomposition of water to produce hydrogen, and the spatial structure of the polyacid and the metal organic complex in the supermolecular structure formed in the invention is favorable for electron conduction of the polyacid and the metal organic complex, so that the catalytic performance of the polyacid-based manganese metal organic hybrid material in the invention is improved, and finally the polyacid molecules and the metal-organic complex have synergistic effect to produce excellent photocatalytic decomposition water to produce hydrogen; powder X-ray diffractionThe X-ray diffraction peak tested by the synthesis method of the step one and the step two is completely consistent with the simulated single crystal X-ray diffraction peak, and the purity of a large amount of synthesized single crystal materials is high. Gas chromatography tests show that the prepared polyacid-based manganese metal organic hybrid material constructed by silicotungstate has the effect of photocatalytic water decomposition hydrogen production, and the hydrogen production rate is 6.31 mu mol g-1·h-1. The embodiment can obtain the polyacid-based manganese metal organic hybrid material constructed by silicotungstate.
The preparation method of the polyacid-based manganese metal organic hybrid material constructed by silicotungstate comprises the following steps:
firstly, preparing a reaction solution with the pH value of 2.0, namely dissolving silicotungstic acid, manganese chloride and a 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand into deionized water to obtain the reaction solution; adjusting the pH value of the reaction solution to 2.0 to obtain a reaction solution with the pH value of 2.0;
the molar ratio of the silicotungstic acid to the metal manganese salt in the step one is 0.1 (0.2-1);
the molar ratio of the silicotungstic acid to the 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand in the step one is 0.1 (0.2-0.5);
the volume ratio of the silicotungstic acid substance in the step one to the distilled water is 0.1mmol (20 ml-35 ml);
secondly, adding the reaction solution with the pH value of 2.0 into a polytetrafluoroethylene reaction kettle, reacting for 3 days at 160 ℃, cooling to room temperature to obtain colorless long-strip crystals, namely the polyacid-based manganese metal organic hybrid material;
the chemical formula of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate in the second step is (H)2SiW12O40)[Mn(pzta)3]2·4H2O, wherein pzta is 5- (2-pyrazinyl) -1,2, 4-triazole; the crystal system is monoclinic; space group is C2/C; unit cell parameters α -90 ° (5), β -107.336 ° (5), γ -90 ° (5),
z＝4。
the third embodiment is different from the second embodiment in that the metal manganese salt in the first embodiment is manganese chloride, manganese nitrate or manganese acetate. The rest is the same as the second embodiment.
Fourth embodiment the present embodiment is different from the second to third embodiments in that the molar ratio of silicotungstic acid to metal manganese salt in the first step is 1: 10. The other embodiments are the same as the second or third embodiment.
Fifth embodiment fifth this embodiment is different from second to fourth embodiments in that the molar ratio of silicotungstic acid to 5- (2-pyrazinyl) -1,2, 4-triazole in step one is 1: 2. The other points are the same as those in the second to fourth embodiments.
Sixth embodiment the present embodiment is different from second to fifth embodiments in that the volume ratio of the amount of the silicotungstic acid substance to distilled water in the first step is 0.1mmol:25 ml. The rest is the same as the second to fifth embodiments.
Seventh embodiment mode A different point of the present embodiment from the second to sixth embodiment modes is that the pH of the reaction solution in the first step is adjusted to 2.0 by using 0.1 to 2mol/L HCl solution and 0.1 to 2mol/L NaOH solution. The rest is the same as the second to sixth embodiments.
In the embodiment, a polyacid-based manganese metal organic hybrid material constructed by silicotungstate is used as a photocatalyst, and a hydrogen test is carried out on hydrogen produced by photocatalytic decomposition under the irradiation of Xe lamps in a 10% triethylamine as a sacrificial agent and acetone and water as solvent solutions.
In the embodiment, a polyacid-based manganese metal organic hybrid material constructed by silicotungstate is used as a photocatalyst, and has excellent photocatalytic effect in a solvent solution with 10% of triethylamine as a sacrificial agent and acetone and water as solvents.
The hydrogen production rate is 6.31 mu mol g after one hydrogen production test per hour-1·h-1。
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is a preparation method of a polyacid-based manganese metal organic hybrid material constructed by silicotungstate, which is completed by the following steps:
firstly, preparing a reaction solution with the pH value of 2.0, namely dissolving 0.1mmol of silicotungstic acid, 1mol of metal manganese salt and 0.2mol of 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand into 35ml of deionized water to obtain a reaction solution, wherein the pH value of the reaction solution is adjusted to 2.0 by using 1mol/L HCl solution and 1mol/L NaOH solution to obtain a reaction solution with the pH value of 2.0;
the volume ratio of the silicotungstic acid substance in the step one to the deionized water is 0.1mmol:35 ml;
secondly, adding the reaction solution with the pH value of 2.0 into a polytetrafluoroethylene reaction kettle, reacting for 3 days at the temperature of 160 ℃, cooling to room temperature to obtain orange-yellow long-strip crystals, namely the polyacid manganese metal organic hybrid material constructed by the silicotungstate.
The analytical data of the X-single crystal diffraction structure of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate prepared in the first embodiment are shown in the table 1, and the used instrument is an ApexII single crystal diffractometer of Bruker company; table one is the analytical data of X-single crystal diffraction structure of polyacid-based manganese metal-organic hybrid materials constructed by silicotungstate prepared in example one.
TABLE 1
aR1＝∑║Fo│─│Fc║/∑│Fo│,bwR2＝∑[w(Fo 2─Fc 2)2]/∑[w(Fo 2)2]1/2
As can be seen from table 1, it is,example A polyacid-based manganese metal organic hybrid material constructed by silicotungstate has a chemical formula of (H)2SiW12O40)[Mn(pzta)3]2·4H2O, molecular formula C36N30H32Mn2SiW12O44Example a polyacid-based manganese metal organic hybrid material constructed by silicotungstate has a spatial polyacid-based manganese metal organic hybrid material structure with the characteristics of metal-organic nanometer supermolecular structure, and polyacid clusters SiW in the structure12The metal organic complexes are free, every three organic ligands are coordinated by nitrogen atoms and metal manganese respectively to form a unit cell structure formed by combining two metal organic complexes and one polyacid cluster through intermolecular force, so that the formed space structure is favorable for fast electron transfer between polyacid and the metal organic complexes, and few stable connection modes are reported to improve the catalytic efficiency of hydrogen production by photocatalytic water decomposition.
X-ray single crystal diffraction analysis shows that the polyacid-based manganese metal organic hybrid material (H) constructed by silicotungstate prepared in the first embodiment2SiW12O40)[Mn(pzta)3]2·4H2The unit cell of O is composed of a multiple negative ion [ SiW ]12O40]2-(abbreviated as SiW)12) FIG. 1 is a schematic structural diagram of a polyacid-based manganese metal organic hybrid material constructed by silicotungstate prepared in the first embodiment, wherein in FIG. 1, 1 is silicon, 2 is oxygen, 3 is tungsten, 4 is manganese, 5 is carbon, 6 is nitrogen, 7 is water, and 8 is hydrogen;
in the structure of the polyacid-based manganese metal organic hybrid material constructed by silicotungstate prepared in the first embodiment, 1 crystallographically independent Mn ion is adopted, and a coordination mode is adopted; mn is in a 6 coordinate linear geometry, coordinated to 3 nitrogen atoms from different pzta organic ligands; the Cu-N bond length range is
All of these bond lengths are within reasonable ranges.
FIG. 2 is a schematic diagram 1 illustrating a process for forming a polyacid-based manganese metal-organic hybrid material structure constructed by silicotungstates prepared in the first embodiment; as can be seen from the figure, the polyacid is a classical Keggin type polyacid SiW12The metal organic complex is formed by bonding metal manganese with three 5- (2-pyrazinyl) -1,2, 4-triazoles through coordination bonds, so that a unit cell structure of a polyacid-based manganese metal organic hybrid material constructed by silicotungstate is formed, and a polyanion [ SiW ] is used as a negative ion12O40]2-(abbreviated as SiW)12) 2 manganese ions, 6 pzta organic ligands and four free waters, and a discrete space structure is formed by space pi-pi accumulation force.
FIG. 3 is an infrared spectrum of a polyacid-based crystalline material with a three-dimensional intercalation structure having the effect of photocatalytic decomposition of water to produce hydrogen prepared in example one; as can be seen from the figure, at 700--1Belongs to polyacid cluster SiW12The stretching vibration of (2); the vibration peak is 1330-1630cm-1The range of (a) is assigned to the stretching vibration peak of the organic ligand pzta. Further, the vibration peak was 3120cm-1Belongs to the vibration expansion peak of water molecules in the compound.
FIG. 4 is a PXRD pattern of a polyacid-based manganese metal-organic hybrid material constructed from silicotungstates prepared in the first example; as shown in the figure, the structure of the polyacid-based manganese metal organic hybrid material is analyzed through X-ray single crystal diffraction, so that a simulated powder X-ray diffraction pattern of the polyacid-based manganese metal organic hybrid material constructed by silicotungstate is simulated. And obtaining the X-ray diffraction pattern of the product through the X-ray powder diffraction experiment. By comparing the experimental spectrogram with the simulated spectrogram, the main peak position and the simulated peak position in the X-ray diffraction spectrogram are basically consistent, which shows that the purity of the material is better.
FIG. 5 is a Mott Schottky electrochemical performance test of the polyacid-based manganese metal-organic hybrid material constructed by silicotungstate prepared in the first embodiment; as shown in the figure, the Mott Schottky curve of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate is measured under the condition that the frequency is 1000Hz, and as can be seen from the figure, the slopes of the straight line parts of all the curves are positive, which indicates that the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate belongs to an n-type semiconductor, the concentration of photo-generated electrons generated after the polyacid-based manganese metal organic hybrid material is excited under the illumination condition is greater than that of photo-generated holes, and if the semiconductor is used as a photocatalyst, the polyacid-based manganese metal organic hybrid material has very good photocatalytic reduction activity. The flat band potential of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate is about-0.863V vs. Ag/AgCl (namely-0.863V vs. NHE), and the conduction band potential is about-0.763V vs. NHE because the conduction band bottom of the n-type semiconductor is generally considered to be more negative 0.1V than the flat band potential.
FIG. 6 is a graph of hydrogen production rate of a polyacid-based manganese metal-organic hybrid material constructed by silicotungstate prepared in example one under 10% triethylamine as a sacrificial reagent for 8 hours. In the experiment, by comparing the influence of various sacrificial agents on the system, the system which takes 10 percent of triethylamine as the sacrificial agent and takes a solvent with the ratio of acetone to water of 2:1 as the photocatalytic water decomposition hydrogen production is finally selected as the catalytic system with the highest hydrogen production, and the average hydrogen production efficiency is 6.31 mu mol g-1·h-1Therefore, the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate is a high-efficiency photocatalyst for photocatalytic water decomposition.
In summary, in this example, a one-step hydrothermal synthesis method is used to successfully synthesize a polyacid-based crystal material with the effect of photocatalytic water decomposition for hydrogen production by using silicotungstic acid, a metal manganese salt and a ligand 5- (2-pyrazinyl) -1,2, 4-triazole.
Claims (8)
1. The preparation method and the photocatalytic application of the polyacid-based manganese metal organic hybrid material constructed by silicotungstate are characterized in that the polyacid-based manganese metal organic hybrid material with the effect of photocatalytic decomposition of water to prepare hydrogen has the chemical formula (H)2SiW12O40)[Mn(pzta)3]2·4H2O, wherein pzta is 5- (2-pyrazinyl) -1,2, 4-triazole; the crystal system is monoclinic; space group is C2/C; unit cell parameters α -90 ° (5), β -107.037 ° (5), γ -90 ° (5),
z＝4。
2. a preparation method of polyacid-based manganese metal organic hybrid material constructed by silicotungstate is characterized in that the preparation method of polyacid-based manganese metal organic hybrid material with photocatalysis water decomposition hydrogen preparation effect is completed according to the following steps:
firstly, preparing a reaction solution with the pH value of 2.0, namely dissolving silicotungstic acid, manganese chloride and a 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand into deionized water to obtain the reaction solution; adjusting the pH value of the reaction solution to 2.0 to obtain a reaction solution with the pH value of 2.0;
the molar ratio of the silicotungstic acid to the metal manganese salt in the step one is 0.1 (0.2-1);
the molar ratio of the silicotungstic acid to the 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand in the step one is 0.1 (0.2-0.5);
the volume ratio of the silicotungstic acid substance in the step one to the distilled water is 0.1mmol (20 ml-35 ml);
secondly, adding the reaction solution with the pH value of 2.0 into a polytetrafluoroethylene reaction kettle, reacting for 3 days at 160 ℃, cooling to room temperature to obtain orange-yellow strip crystals, namely the polyacid-based manganese metal organic hybrid material;
the chemical formula of the polyacid-based manganese metal organic hybrid material constructed by the silicotungstate in the second step is (H)2SiW12O40)[Mn(pzta)3]2·4H2O, wherein pzta is 5- (2-pyrazinyl) -1,2, 4-triazole; the crystal system is monoclinic; space group is C2/C; unit cell parameters α -90 ° (5), β -107.037 ° (5), γ -90 ° (5),
z＝4。
3. the method for preparing polyacid-based manganese metal-organic hybrid materials constructed by silicotungstates according to claim 2, wherein the metal salt in the step one is manganese chloride, manganese nitrate or manganese acetate.
4. The method for preparing polyacid-based manganese metal-organic hybrid materials constructed by silicotungstates according to claim 2, characterized in that the molar ratio of silicotungstic acid to metal manganese salt in the step one is 1: 10.
5. The method for preparing polyacid-based manganese metal-organic hybrid materials constructed by silicotungstates according to claim 2, wherein the molar ratio of silicotungstic acid to 5- (2-pyrazinyl) -1,2, 4-triazole organic ligand in the step one is 1: 2.
6. The method for preparing polyacid-based manganese metal-organic hybrid materials constructed by silicotungstates according to claim 2, wherein the volume ratio of the amount of silicotungstic acid substance to distilled water in the step one is 0.1mmol:25 ml.
7. The method for preparing polyacid-based manganese metal-organic hybrid material constructed by silicotungstate according to claim 2, wherein the pH value of the reaction solution in step one is adjusted to 2.0 by using 0.1-2 mol/L HCl solution and 0.1-2 mol/L NaOH solution.
8. The preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate are characterized in that polyacid molecules in the structures of most of the conventional materials are not photosensitive and do not contain metal atoms with reducibility, and the semiconductor structure formed by polyacid and metal organic complexes in the hybrid material has wider forbidden bandwidth and more than zero conduction band, so that the polyacid-based manganese metal organic hybrid material does not have the property of photolysis water hydrogen production, while the polyacid-based manganese metal organic hybrid material constructed by silicotungstate, prepared by the invention, contains the silicotungstate with good photosensitivity and the manganese atoms with reducibility, has narrower forbidden bandwidth and less than zero conduction band in the semiconductor structure formed by polyacid and metal organic complexes in the hybrid material, and has good photocatalytic water decomposition effect, and the supermolecular structure formed in the invention and the spatial structure of the polyacid and the metal organic complex are beneficial to the electron conduction of the polyacid and the metal organic complex, so that the catalytic performance of the polyacid-based manganese metal organic hybrid material in the invention is improved, and finally, the polyacid molecules and the metal-organic complex are synergistic to generate excellent hydrogen production performance by photocatalytic water decomposition.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011385819.6A CN112457348A (en) | 2020-12-01 | 2020-12-01 | Preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011385819.6A CN112457348A (en) | 2020-12-01 | 2020-12-01 | Preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112457348A true CN112457348A (en) | 2021-03-09 |
Family
ID=74805144
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011385819.6A Pending CN112457348A (en) | 2020-12-01 | 2020-12-01 | Preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112457348A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380336A (en) * | 2021-12-10 | 2022-04-22 | 华南理工大学 | Keggin type manganese tungstate with manganese center as well as preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009155185A1 (en) * | 2008-06-20 | 2009-12-23 | Exxonmobil Chemical Patents Inc. | Ruthenium-containing polyoxotungstates, their preparation and use as catalysts in the oxidation of organic substrates |
| JP2010180199A (en) * | 2009-01-07 | 2010-08-19 | Kuraray Co Ltd | Metal complex and method for producing the same |
| US20110118490A1 (en) * | 2009-11-19 | 2011-05-19 | Hwang Young Kyu | Porous Organic-Inorganic Hybrid Materials with Crystallinity and Method for Preparing Thereof |
| CN110227555A (en) * | 2019-07-08 | 2019-09-13 | 哈尔滨理工大学 | A kind of preparation of polyacid base cobalt metal organic Hybrid Materials and photocatalytic applications |
-
2020
- 2020-12-01 CN CN202011385819.6A patent/CN112457348A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009155185A1 (en) * | 2008-06-20 | 2009-12-23 | Exxonmobil Chemical Patents Inc. | Ruthenium-containing polyoxotungstates, their preparation and use as catalysts in the oxidation of organic substrates |
| JP2010180199A (en) * | 2009-01-07 | 2010-08-19 | Kuraray Co Ltd | Metal complex and method for producing the same |
| US20110118490A1 (en) * | 2009-11-19 | 2011-05-19 | Hwang Young Kyu | Porous Organic-Inorganic Hybrid Materials with Crystallinity and Method for Preparing Thereof |
| CN110227555A (en) * | 2019-07-08 | 2019-09-13 | 哈尔滨理工大学 | A kind of preparation of polyacid base cobalt metal organic Hybrid Materials and photocatalytic applications |
Non-Patent Citations (1)
| Title |
|---|
| BONAN LI ET AL.: "Rational regulation of transition metals in polyoxometalate hybrids without noble metal assistance for efficient light-driven H2 production" * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114380336A (en) * | 2021-12-10 | 2022-04-22 | 华南理工大学 | Keggin type manganese tungstate with manganese center as well as preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110227555B (en) | Preparation and photocatalytic application of polyacid-based cobalt metal organic hybrid material | |
| CN108997594B (en) | Polyacid-based metal organic framework crystal material with polyacid as template | |
| Chinnadurai et al. | Mn-Co bimetallic phosphate on electrodeposited PANI nanowires with composition modulated structural morphology for efficient electrocatalytic water splitting | |
| Wang et al. | A highly efficient Fe-doped Ni 3 S 2 electrocatalyst for overall water splitting | |
| CN110227556B (en) | Preparation and photocatalytic application of polyacid-based iron metal organic hybrid material | |
| Sun et al. | Surface modification of NiCo2O4 nanowires using organic ligands for overall water splitting | |
| Li et al. | Self-ZIF template-directed synthesis of a CoS nanoflake array as a Janus electrocatalyst for overall water splitting | |
| Shuai et al. | Recent developments of MXene-based catalysts for hydrogen production by water splitting | |
| CN110777393B (en) | Nickel-vanadium double metal hydroxide electrode for wide-range full-hydrolysis and preparation method and application thereof | |
| CN113457742B (en) | Preparation and photocatalytic application of phosphomolybdic acid constructed polyacid-based cadmium metal hybrid material | |
| Wan et al. | Boosting nitrate electroreduction to ammonia on NbO x via constructing oxygen vacancies | |
| CN110026241B (en) | Three-dimensional polyacid-based nickel metal-organic crystalline catalytic material and preparation method thereof | |
| CN110841661A (en) | Preparation method and application of 1T-2H molybdenum disulfide @ cadmium sulfide composite nanomaterial | |
| CN112680746B (en) | ZIF-67@ MXene composite material, and preparation method and application thereof | |
| Xu et al. | Interface engineering of copper-cobalt based heterostructure as bifunctional electrocatalysts for overall water splitting | |
| Kwon et al. | High performance transition metal-based electrocatalysts for green hydrogen production | |
| Ji et al. | Full water splitting by a nanoporous CeO 2 nanowire array under alkaline conditions | |
| CN114685805B (en) | Preparation method for directly synthesizing MOF material for electrocatalytic carbon dioxide reduction at room temperature | |
| Zhao et al. | Antiperovskite nitride Cu3N nanosheets for efficient electrochemical oxidation of methanol to formate | |
| Wu et al. | Amorphous nickel–iron hydroxide nanosheets for effective electroreduction of nitrate to ammonia | |
| Zhang et al. | Hybridization of Mn/Ta bimetallic oxide and mesh-like porous bio-carbon for boosting copper reduction for D35/Y123-sensitized solar cells and hydrogen evolution | |
| Jiang et al. | Interfacial engineering of metal–organic framework derived hierarchical CoP–Ni 5 P 4 nanosheet arrays for overall water splitting | |
| CN112457348A (en) | Preparation and photocatalytic application of polyacid-based manganese metal organic hybrid material constructed by silicotungstate | |
| Chen et al. | Enhanced electrocatalytic performance of TiO 2 nanoparticles by Pd doping toward ammonia synthesis under ambient conditions | |
| CN110854396A (en) | PtAg nanocrystalline with porous double-hollow-sphere structure and preparation method and application thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210309 |
|
| RJ01 | Rejection of invention patent application after publication |