CN109999837A - A kind of preparation method of the metal sulfide catalyst of surface defect state modification - Google Patents
A kind of preparation method of the metal sulfide catalyst of surface defect state modification Download PDFInfo
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- CN109999837A CN109999837A CN201910359800.5A CN201910359800A CN109999837A CN 109999837 A CN109999837 A CN 109999837A CN 201910359800 A CN201910359800 A CN 201910359800A CN 109999837 A CN109999837 A CN 109999837A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 230000007547 defect Effects 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 229910052976 metal sulfide Inorganic materials 0.000 title claims abstract description 25
- 230000004048 modification Effects 0.000 title claims abstract description 19
- 238000012986 modification Methods 0.000 title claims abstract description 19
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 36
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims abstract description 22
- 235000018417 cysteine Nutrition 0.000 claims abstract description 22
- UVLYPUPIDJLUCM-UHFFFAOYSA-N indium;hydrate Chemical compound O.[In] UVLYPUPIDJLUCM-UHFFFAOYSA-N 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 9
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 9
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims abstract description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 238000001291 vacuum drying Methods 0.000 claims abstract description 4
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 13
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical group OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 30
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 15
- 239000008367 deionised water Substances 0.000 abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000011701 zinc Substances 0.000 description 152
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 31
- 230000001699 photocatalysis Effects 0.000 description 24
- 238000007146 photocatalysis Methods 0.000 description 23
- 230000000694 effects Effects 0.000 description 17
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 16
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 230000008859 change Effects 0.000 description 12
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 11
- 239000008103 glucose Substances 0.000 description 11
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 11
- 108010020943 Nitrogenase Proteins 0.000 description 10
- 235000019445 benzyl alcohol Nutrition 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 10
- 238000005859 coupling reaction Methods 0.000 description 9
- 238000004435 EPR spectroscopy Methods 0.000 description 8
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 230000001052 transient effect Effects 0.000 description 8
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 description 7
- 239000002028 Biomass Substances 0.000 description 7
- 230000002950 deficient Effects 0.000 description 7
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000010189 synthetic method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 229910052725 zinc Inorganic materials 0.000 description 3
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GJWAPAVRQYYSTK-UHFFFAOYSA-N [(dimethyl-$l^{3}-silanyl)amino]-dimethylsilicon Chemical compound C[Si](C)N[Si](C)C GJWAPAVRQYYSTK-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000001131 transforming effect Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical group O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000004178 biological nitrogen fixation Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- -1 glucose Chemical compound 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000026676 system process Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of the metal sulfide catalyst of surface defect state modification, include the following steps: that (1) weighs nitrate, nitric hydrate indium or lanthanum nitrate respectively or three kinds of zinc nitrate, cysteine raw materials are placed in the beaker equipped with deionized water, stirring and dissolving obtains mixed liquor；(2) mixed liquor in step (1) is transferred in polytetrafluoroethyllining lining respectively, is sealed, make the metal sulfide catalyst being washed with deionized, vacuum drying is modified to get surface defect state after hydro-thermal process.Catalyst of the invention improves N2Molecule reactivity promotes the progress of fixed nitrogen reaction.Synthetic route is simple, it is easy, there is versatility.
Description
Technical field
The present invention relates to the preparation method of catalyst, in particular to a kind of metal sulfide catalyst of surface defect state modification
The preparation method of agent.
Background technique
Conductor photocatalysis fixed nitrogen causes global very big concern because of the characteristic of its high-efficiency cleaning.With biological nitrogen fixation enzyme
Similar, photocatalytic process can be under mild conditions by N using sun phot-luminescence catalyst2It is reduced to NH3, for more cleaning and
More sustainable NH3Production provides a Non-carbonized road.Photocatalysis technology can directly convert solar energy into chemical energy,
One kind, which is provided, for reduction synthesis ammonia energy consumption has very much promising method.However, the superelevation bond energy of three key of nitrogen-nitrogen makes nitrogen point
Stable chemical characteristic is revealed in daughter, is difficult to activate nitrogen molecular so as to cause conventional catalysis material.Therefore, exploitation is efficient
Fixed nitrogen synthesis ammonia photochemical catalyst still faces huge challenge.
Summary of the invention
Goal of the invention: it is an object of the present invention to provide a kind of preparation sides of the metal sulfide catalyst of surface defect state modification
Method, the catalyst improve N2Molecule reactivity promotes the progress of fixed nitrogen reaction.
Technical solution: the present invention provides a kind of preparation method of the metal sulfide catalyst of surface defect state modification, packet
Include following steps:
(1) nitrate, nitric hydrate indium, cysteine are weighed respectively to be placed in the beaker equipped with deionized water, are stirred molten
Solution, obtains mixed liquor；
(2) mixed liquor in step (1) is transferred in polytetrafluoroethyllining lining respectively, is sealed, used after hydro-thermal process
The catalyst that deionized water washing, vacuum drying are modified to get different surface defect states.
Further, the temperature of hydro-thermal process is 200 DEG C in the step (1).Nitrate is nitric acid in the step (1)
Zinc.
Further, zinc nitrate, nitric hydrate indium and the cysteine mole of the step (1) be respectively 1.5mmol,
1mmol and 3mmol, the product in step (2) are Zn- defect Zn3In2S6.The zinc nitrate of the step (1), nitric hydrate indium and
Cysteine mole is respectively 2mmol, 1mmol and 3.5mmol, and the product in step (2) is Zn- defect Zn4In2S7.It is described
Zinc nitrate, nitric hydrate indium and the cysteine mole of step (1) are respectively 2.5mmol, 1mmol and 4mmol, step (2)
In product be Zn- defect Zn5In2S8。
Further, nitrate is cadmium nitrate in the step (1).
Further, cadmium nitrate, nitric hydrate indium and the cysteine mole of the step (1) be respectively 0.5mmol,
1mmol and 2mmol, the product in step (2) are Cd defect-CdIn2S4.Cadmium nitrate, lanthanum nitrate and half Guang of the step (1)
Propylhomoserin mole is respectively 0.5mmol, 1mmol and 2mmol, and the product in step (2) is Cd defect-CdLa2S4.The step
(1) cadmium nitrate, lanthanum nitrate and cysteine mole is respectively 0.5mmol, 1mmol and 2mmol, the product in step (2)
For Cd defect-CdLa2S4.Cadmium nitrate, zinc nitrate and the cysteine mole of the step (1) be respectively 0.75mmol,
0.25mmol and 2mmol, the product in step (2) are Zn defect-Cd0.75Zn0.25S。
In above-mentioned technical proposal, the surface defect site of catalyst can be used as the active site of nitrogen molecular chemisorption,
Local can be transferred into the antibonding π track of absorption nitrogen molecular in the electronics of fault location simultaneously, to realize to three key of nitrogen-nitrogen
The separation of attenuation and photo-generate electron-hole.Promote photocatalysis N2The promotion of reduction reaction efficiency.
The utility model has the advantages that constructing for catalyst surface defect state of the invention is conducive to N2The absorption and activation of molecule and light
The separation of raw electron-hole, improves nitrogen-fixing efficiency.And this synthetic route it is simple, it is easy, have versatility, can promote and be suitable for
Synthesize other a variety of transient metal sulfide semiconductors.
Detailed description of the invention
Fig. 1 is the Zn defect-Zn of Examples 1 and 2 preparation3In2S6And Zn3In2S6The X-ray powder diffraction figure of catalyst；
Fig. 2 is that embodiment 1 prepares Zn defect-Zn3In2S6(a) TEM and (b) HRTEM scheme；
Fig. 3 is that embodiment 2 prepares Zn3In2S6HRTEM figure；
Zn defect-the Zn of Fig. 4 Examples 1 and 2 preparation3In2S6And Zn3In2S6The EPR spectrogram of catalyst；
Fig. 5 is the Zn defect-Zn of Examples 1 and 2 preparation3In2S6And Zn3In2S6Coupled biological matter alcohol is selectively convertered double
Ergasia photocatalysis to selectively Oxybenzene methyl alcohol is to benzaldehyde and nitrogenase activity figure；
Fig. 6 is the Zn defect-Zn prepared in embodiment 13In2S6Pure aquatic system photocatalysis nitrogenase activity figure；
Fig. 7 is the Zn defect-Zn prepared in embodiment 13In2S6Sacrifice agent system photocatalysis nitrogenase activity figure；
Fig. 8 is the Zn defect-Zn prepared in embodiment 13In2S6Difunctional system photocatalysis biomass glucose selective
Nitrogenase activity figure while conversion prepares 5 hydroxymethyl furfural；
Fig. 9 be respectively embodiment 6, embodiment 1, embodiment 6, embodiment 6, embodiment 11, embodiment 10, embodiment 13,
Zn prepared by embodiment 123In2S6, Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn defect-Cd0.75Zn0.25S、CdIn2S4、Cd
Defect-CdIn2S4、CdLa2S4, Cd defect-CdLa2S4The X-ray powder diffraction figure of catalyst；
Figure 10 be respectively embodiment 6, embodiment 1, embodiment 6, embodiment 6, embodiment 11, embodiment 10, embodiment 13,
Zn prepared by embodiment 123In2S6, Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn defect-Cd0.75Zn0.25S、CdIn2S4、Cd
Defect-CdIn2S4、CdLa2S4, Cd defect-CdLa2S4The EPR spectrogram of catalyst；
Figure 11 be respectively embodiment 6, embodiment 1, embodiment 6, embodiment 6, embodiment 11, embodiment 10, embodiment 13,
Zn prepared by embodiment 123In2S6, Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn defect-Cd0.75Zn0.25S、CdIn2S4、Cd
Defect-CdIn2S4、CdLa2S4, Cd defect-CdLa2S4The pure aquatic system photocatalysis nitrogenase activity figure of catalyst；
Figure 12 is Cd prepared by embodiment 60.75Zn0.25S and Zn defect-Cd0.75Zn0.25S coupled biological matter alcohol selectively turns
Change difunctional system photocatalysis to selectively Oxybenzene methyl alcohol to benzaldehyde and nitrogenase activity figure；
Figure 13 is Zn defect-Cd prepared by embodiment 60.75Zn0.25The difunctional system photocatalysis biomass glucose selection of S
Nitrogenase activity figure while property conversion prepares 5 hydroxymethyl furfural；
Figure 14 is the mechanism schematic diagram of photocatalysis fixed nitrogen reactivity of the present invention.
Specific embodiment
Transient metal sulfide can be abbreviated as TMDs, can be abbreviated as defect-TMDs containing defective transient metal sulfide.
Embodiment 1
The present embodiment prepares Zn defect-Zn as follows3In2S6(when x=3) catalyst:
Step 1,1.5mmol zinc nitrate, 1mmol nitric hydrate indium and 3mmol cysteine are weighed respectively in equipped with 60mL
In the beaker of deionized water, stir to dissolve；
Step 2, mixed liquor in step 1 is transferred in 100ml polytetrafluoroethyllining lining, is sealed, 200 DEG C of hydro-thermal, 20 is small
When after, by deionized water washing, vacuum drying is up to Zn defect-Zn3In2S6Catalyst.
Catalyst (transient metal sulfide (TMDs) of surface defect modification) Zn defect-of other surface defect modifications
ZnxIn2S3+x(x=1-5) etc. it can be made by feed change and process conditions using above-mentioned preparation method.Wherein, metallic element
Raw material is that its nitrate, raw material proportioning are all made of the atomic composition ratio of TMDs, and other conditions are constant.
Embodiment 2
The present embodiment prepares Zn- defect ZnIn as follows2S4(when x=1) catalyst:
Zn- defect ZnIn2S4Synthesis: 0.5mmol zinc nitrate, 1mmol nitric hydrate indium and 2mmol cysteine；It is other
Condition is constant.
With Zn defect-Zn in embodiment 13In2S6The synthetic method of catalyst is the same, and different is the throwing of feed change
Enter amount ratio.
Embodiment 3
The present embodiment prepares Zn- defect Zn as follows2In2S5(when x=2) catalyst:
Zn- defect ZnIn2S5Synthesis: 1mmol zinc nitrate, 1mmol nitric hydrate indium and 2.5mmol cysteine；It is other
Condition is constant.
With Zn defect-Zn in embodiment 13In2S6The synthetic method of catalyst is the same, and different is the throwing of feed change
Enter amount ratio.
Embodiment 4
The present embodiment prepares Zn- defect Zn as follows4In2S7(when x=4) catalyst:
Zn- defect ZnIn2S7Synthesis: 2mmol zinc nitrate, 1mmol nitric hydrate indium and 3.5mmol cysteine；It is other
Condition is constant.
With Zn defect-Zn in embodiment 13In2S6The synthetic method of catalyst is the same, and different is the throwing of feed change
Enter amount ratio.
Embodiment 5
The present embodiment prepares Zn- defect Zn as follows5In2S8(when x=5) catalyst:
Zn- defect ZnIn2S8Synthesis: 2.5mmol zinc nitrate, 1mmol nitric hydrate indium and 4mmol cysteine；It is other
Condition is constant.
With Zn defect-Zn in embodiment 13In2S6The synthetic method of catalyst is the same, and different is the throwing of feed change
Enter amount ratio.
Embodiment 6
This example is same as Example 1, the difference is that hydrothermal temperature is 180 DEG C in step 2, Zn is prepared3In2S6
Catalyst.
Zn defect-Zn prepared by the embodiment of the present invention 13In2S6The Zn prepared with embodiment 63In2S6Catalyst carries out table
Sign, as a result as shown in Figure 1, Figure 2, Figure 3 and Figure 4.Wherein, Fig. 1 is X-ray diffraction (XRD) figure, Zn defect-Zn3In2S6With
Zn3In2S6All diffraction maximums correspond to hexagonal phase Zn well in diffraction pattern3In2S6.It is released by figure,α=β=90 °, γ=120 °.Illustrate the Zn3In of pure phase2S6Successfully prepared, and Zn-
Defect does not cause the generation of novel substance phase.
Fig. 2 is Zn defect-Zn3In2S6Transmission electron microscope (TEM) and high-resolution-ration transmission electric-lens (HRTEM) figure, as seen from the figure
Sample is ultra-thin two-dimension laminated structure ((a) figure), Zn defect-Zn3In2S6In the high-visible (arrow of the lattice fringe containing defect state
Head is signified, (b) figure).And Zn3In2S6Lattice fringe complete display (Fig. 3) and Zn defect-Zn3In2S6HRTEM figure at
Sharp contrast.
In order to further confirm that the presence of defect state, electron paramagnetic resonance (EPR) are the tools for characterizing fault in material,
It is seen from Fig. 3, Zn3In2S6There is no an apparent peak EPR, and Zn defect-Zn3In2S6The peak EPR it is sharp obvious and the g factor is
2.003, illustrate Zn prepared by this example 13In2S6Catalyst surface Zn defect rich in, and Zn prepared by example 63In2S6
Catalyst does not have Zn defect (in experimental condition optimization, it has been found that cannot synthesize defect state lower than 200 DEG C
Zn3In2S6).By analyzing above, it is known that passed through by this method and change the preparation that reaction temperature can be easy containing defective
Two-dimensional TM Ds.
In order to investigate the universality of this experimental method, a series of surface defects modifications have been synthesized by changing reactant feed
Transient metal sulfide (TMDs) (catalyst): Cd defect-CdIn2S4, Cd defect-CdLa2S4, Zn defect-CdxZn1-xS(x
=0-1) and Zn defect-ZnxIn3S3+x(x=1-5).Wherein metallic element raw material is that its nitrate, raw material proportioning are all made of
The atomic composition ratio of TMDs, other conditions are constant.
Such as: Zn defect-Cd0.5Zn0.5The synthesis of S: half Guang ammonia of 0.5mmol cadmium nitrate, 0.5mmol zinc nitrate and 2mmol
Acid；Other conditions are in the same manner as in Example 1.
Such as: Zn defect-Cd0.75Zn0.25The synthesis of S: half Guang of 0.75mmol cadmium nitrate, 0.25mmol zinc nitrate and 2mmol
Propylhomoserin；Other conditions are in the same manner as in Example 1.
When hydrothermal temperature is changed to 180 DEG C in the step 2 of above-mentioned condition, raw material other conditions are constant, and Cd is made0.75Zn0.25S。
Embodiment 7
This example be difunctional reaction system building (mixed solution of biomass and water containing alcoholic extract hydroxyl group use benzene first
Alcohol), detailed step is as follows:
Step 1, by the Zn defect-Zn of 0.03g3In2S6The benzyl alcohol of catalyst and 50mL be added to three mouthfuls of 100mL it is poly-
In tetrafluoroethene reaction kettle；
Step 2, N is passed through into reaction kettle2Emptying wherein after air, keeps N in reaction kettle2Pressure is about 0.2Mpa；
Step 3, visible light source is opened, every 1 hour extraction 5mL after stir about 0.5h adsorption/desorption balance under dark-state
Reaction solution is centrifugated, liquid product such as ammonia, aldehyde etc. in analysis detection reaction solution.
Embodiment 8
This example is pure water N2Reduction, this example is same as Example 7, the difference is that in step 1 be added 50mL go from
Sub- water.
Embodiment 9
This example is sacrifice agent system N2Reduction, step is same as Example 8, the difference is that 50mL is added in step 1
Methanol aqueous solution (volumn concentration 20%).
The result of embodiment 7, embodiment 8 and embodiment 9 is respectively such as Fig. 5, Fig. 6 and Fig. 7.As seen from Figure 5, pure Zn3In2S6
Selective oxidation activity is illustrated only, benzyl alcohol selective can be oxidized to benzaldehyde, but N cannot be restored2.This explanation
Zn3In2S6With suitable valence band position (Hole oxidation ability) can selective oxidation benzyl alcohol to benzaldehyde, although its conduction band
Position is relatively negative, but cannot restore N2, this also illustrates N2The extremely strong stability of molecule is difficult to activate.And Zn defect-Zn3In2S6It is (real
Apply example 3) benzyl alcohol selective can be not only oxidized to benzaldehyde, but also can be efficiently by N2It is reduced to NH3, yield reaches
0.95mmol/g/h.This is because one side benzyl alcohol dehydrogenation-N2Hydrogenation coupled reaction system can significantly improve pure aquatic system N2
The thermodynamics (G ° of Gibbs free energy Δ greatly reduces) of reduction, another aspect Zn- defect can activate N2Molecule and enrichment light
Raw electronics, intensified response dynamics.In order to illustrate the advantage of this difunctional coupling reaction system, we have done two groups to according to the facts
It tests: first is that pure aquatic system N2Restore (Fig. 6) and sacrifice agent system N2It restores (Fig. 7).Zn defect-Zn3In2S6Though in pure aquatic system
N can so be restored2Prepare NH3, but yield is extremely low.By adding hole sacrifice agent, although photocatalytic activity obtains significantly
It improves, but the unfriendly substance of the environment such as CO, CO2 and HCHO can be discharged.By result above analysis as it can be seen that this patent proposes
The preparation method of the TMDs of surface defect state modification and the novel N of design2Restore difunctional photocatalysis coupled reaction system be can
Row.
In order to further expand the versatility that the surface defect state of this patent proposition modifies TMDs preparation method, we pass through
Change reaction raw materials, is successfully prepared Cd defect-CdIn2S4, Cd defect-CdLa2S4, Zn defect-CdxZn1-xS (x=0-1) and
Zn defect-ZnxIn2S3+x(x=1-5) photochemical catalysts such as.And in N2Restore shown in difunctional light-catalyzed reaction system compared with
Good selective oxidation and N2Reducing property.
In order to further investigate the practical operability of this programme, we are using the biomass glucose being more easy to get extensively
For raw material, Zn defect-Zn has been investigated3In2S6Photocatalysis to selectively transforming glucose and N2Restore the property of difunctional reaction system
Energy.As shown in figure 8, glucose is slowly converted into high valuable chemicals 5 hydroxymethyl furfural at the beginning, without NH3It is raw
At.Because photo-excited semiconductor generates electron-hole pair, photohole selectivity in this difunctional coupling reaction system
It aoxidizes hydroxyl dehydrogenation and generates carbonyls and release hydrogen；The hydrogen and N being then released2It is restored by light induced electron and generates NH3(figure
9), therefore reaction has hysteresis effect.With the extension of reaction time, 5 hydroxymethyl furfural and NH3Yield grow steadily, again
Demonstrate the potential value of this difunctional coupling reaction system.
From the above it is found that the N that the present invention constructs2It is easy to restore difunctional light-catalyzed reaction system process flow, together
When not only can effectively realize N2Resource utilization, and hydrocarbon C can be preparedxHyOz, catalyst pair of the invention
This N2It restores difunctional light-catalyzed reaction and shows extraordinary activity.The industrialization of this difunctional light-catalyzed reaction system thus is answered
With more abundant catalyst choice and development space is provided, such as selected according to the difference of reaction substrate and the different of target product
Select different catalyst or building band band transfer and Z-type photocatalysis composite.
Embodiment 10
The present embodiment prepares Cd defect-CdIn as follows2S4Catalyst:
Cd defect-CdIn2S4Synthesis: 0.5mmol cadmium nitrate, 1mmol nitric hydrate indium and 2mmol cysteine；It is other
Condition is in the same manner as in Example 1.
Embodiment 11
The present embodiment prepares CdIn as follows2S4Catalyst:
This example is same as in Example 10, the difference is that hydrothermal temperature is 180 DEG C in step 2, CdIn is prepared2S4
Catalyst.
Embodiment 12
The present embodiment prepares Cd defect-CdLa as follows2S4Catalyst:
Cd defect-CdIn2S4Synthesis: 0.5mmol cadmium nitrate, 1mmol lanthanum nitrate and 2mmol cysteine；Other conditions
In the same manner as in Example 1.
Embodiment 13
The present embodiment prepares CdLa as follows2S4Catalyst:
This example is identical as embodiment 12, the difference is that hydrothermal temperature is 180 DEG C in step 2, CdLa is prepared2S4
Catalyst.
Embodiment 14
To embodiment 6, embodiment 1, embodiment 6, embodiment 6, embodiment 11, embodiment 10, embodiment 13, embodiment 12
The Zn of preparation3In2S6, Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn defect-Cd0.75Zn0.25S、CdIn2S4, Cd defect-
CdIn2S4、CdLa2S4, Cd defect-CdLa2S4Catalyst carries out X-ray powder diffraction analysis, the Transition Metal Sulfur as a result prepared
Compound (TMDs) Zn3In2S6、Cd0.75Zn0.25S、CdIn2S4And CdLa2S4XRD spectra show preparation transient metal sulfide
It is pure hexagonal phase.And-the Zn containing defective transient metal sulfide (V-TMDs) Zn defect3In2S6, Zn defect-
Cd0.75Zn0.25S, Cd defect-CdIn2S4With Cd defect-CdLa2S4The XRD spectra of catalyst and Transition Metal Sulfur without defect
The spectrogram of compound is essentially the same, without significant change, illustrates that the crystal phase structure containing defective transient metal sulfide is not sent out
Changing.
Embodiment 15
Respectively to embodiment 6, embodiment 1, embodiment 6, embodiment 6, embodiment 11, embodiment 10, embodiment 13, implementation
Zn prepared by example 123In2S6, Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn defect-Cd0.75Zn0.25S、CdIn2S4, Cd defect-
CdIn2S4、CdLa2S4, Cd defect-CdLa2S4Catalyst carries out EPR spectrum analysis, and in order to confirm the presence of defect state, electronics is suitable
Magnetic resonance (EPR) is the tool for characterizing fault in material, and in terms of Figure 10, TMDS does not have an apparent peak EPR, and V-TMDs
The peak EPR is sharp, illustrates the TMDS catalyst surface prepared under the conditions of 200 DEG C Zn or Cd defect rich in, and at 180 DEG C
Under the conditions of the TMDs catalyst for preparing there is no defect (in experimental condition optimization, it has been found that cannot synthesize lower than 200 DEG C scarce
Fall into the TMDs of state).By analyzing above, it is known that passed through by this method and change the preparation that reaction temperature can be easy containing defective
Two-dimensional TM Ds.
Embodiment 16
To Zn prepared in the above embodiments3In2S6, Zn defect-Zn3In2S6、Cd0.75Zn0.25S, Zn defect-
Cd0.75Zn0.25S、CdIn2S4, Cd defect-CdIn2S4、CdLa2S4, Cd defect-CdLa2S4It is living that catalyst carries out photocatalysis fixed nitrogen
Property analysis；In order to investigate superiority of the V-TMDs in photocatalysis fixed nitrogen, their performance, Figure 11 are had detected under pure aquatic system
Shown, under identical condition, the TMDs without defect does not show activity to photocatalysis fixed nitrogen, and contains defective V-TMDs
It is then demonstrated by apparent photocatalysis nitrogenase activity, wherein Zn defect-Cd0.75Zn0.25The activity of S is best.
Embodiment 17
To Cd prepared in the above embodiments0.75Zn0.25S and Zn defect-Cd0.75Zn0.25S coupled biological matter alcohol selectively turns
Change difunctional system photocatalysis to selectively Oxybenzene methyl alcohol to analyze to benzaldehyde and nitrogenase activity；It is pure as shown in Figure 12
Cd0.75Zn0.25S illustrates only selective oxidation activity, benzyl alcohol selective can be oxidized to benzaldehyde, but cannot restore
N2.This illustrates Cd0.75Zn0.25S have suitable valence band position (Hole oxidation ability) can selective oxidation benzyl alcohol to benzene first
Aldehyde cannot restore N although its conduction band position is relatively negative2, this also illustrates N2The extremely strong stability of molecule is difficult to activate.And Zn is lacked
Fall into-Cd0.75Zn0.25Benzyl alcohol selective can be not only oxidized to benzaldehyde by S, but also can be efficiently by N2It is reduced to NH3,
Yield is up to 1030 μm of ol/g/h.This is because one side benzyl alcohol dehydrogenation-N2Hydrogenation coupled reaction system can significantly improve pure
Aqueous systems N2(G ° of Gibbs free energy Δ greatly reduces the thermodynamics of reduction, and the Gibbs free energy of pure water photocatalysis fixed nitrogen is about
For 681.1KJ/mol；And the Gibbs free energy of benzyl alcohol coupling photocatalysis fixed nitrogen is about 51.1KJ/mol), another aspect Zn-
Defect can activate N2Molecule and enrichment light induced electron, intensified response dynamics.
Embodiment 18
Zn defect-Cd prepared by embodiment 60.75Zn0.25The difunctional system photocatalysis biomass glucose selective of S turns
Nitrogenase activity is analyzed while change prepares 5 hydroxymethyl furfural.
In order to further investigate the practical operability of this programme, use the biomass glucose being more easy to get extensively for original
Material, has investigated Zn defect-Cd0.75Zn0.25S photocatalysis to selectively transforming glucose and N2Restore the performance of difunctional reaction system.
As shown in figure 13, glucose is slowly converted into high valuable chemicals 5 hydroxymethyl furfural at the beginning, without NH3It generates.
Because photo-excited semiconductor generates electron-hole pair, photohole selective oxidation in this difunctional coupling reaction system
Hydroxyl dehydrogenation generates carbonyls and release hydrogen；The hydrogen and N being then released2It is restored by light induced electron and generates NH3(Figure 14),
Therefore reaction has hysteresis effect.With the extension of reaction time, 5 hydroxymethyl furfural and NH3Yield grow steadily, demonstrate,prove again
The potential using value containing defective TMDs (being denoted as V-TMDs) is illustrated.Several metal sulfide catalysts containing defect above-mentioned
In agent, Zn defect-Cd0.75Zn0.25S is demonstrated by preferable activity, it is further coupled fixed nitrogen with benzyl alcohol, finds its activity
It is significantly better than pure aquatic system；Benzyl alcohol is further changed to more extensive biomass alcohol such as glucose, finds Zn defect-
Cd0.75Zn0.25S can also realize glucose and N2The coupling reaction of reduction.
Claims (10)
1. a kind of preparation method of the metal sulfide catalyst of surface defect state modification, characterized by the following steps:
(1) weigh nitrate, nitric hydrate indium or lanthanum nitrate respectively or three kinds of zinc nitrate, cysteine raw materials be placed in equipped with go from
In the beaker of sub- water, stirring and dissolving obtains mixed liquor；
(2) mixed liquor in step (1) is transferred in polytetrafluoroethyllining lining respectively, is sealed, after hydro-thermal process using go from
The metal sulfide catalyst that sub- water washing, vacuum drying are modified to get surface defect state.
2. the preparation method of the metal sulfide catalyst of surface defect state modification according to claim 1, feature exist
In: the temperature of hydro-thermal process is 200 DEG C in the step (2).
3. the preparation method of the metal sulfide catalyst of surface defect state modification according to claim 1, feature exist
In: nitrate is zinc nitrate in the step (1).
4. according to claim 1 or the preparation method of the metal sulfide catalyst of 3 described in any item surface defect states modification,
It is characterized by: zinc nitrate, nitric hydrate indium and the cysteine mole of the step (1) are respectively 1.5mmol, 1mmol
And 3mmol.
5. according to claim 1 or the preparation method of the metal sulfide catalyst of 3 described in any item surface defect states modification,
It is characterized by: zinc nitrate, nitric hydrate indium and the cysteine mole of the step (1) be respectively 2mmol, 1mmol and
3.5mmol。
6. according to claim 1 or the preparation method of the metal sulfide catalyst of 3 described in any item surface defect states modification,
It is characterized by: zinc nitrate, nitric hydrate indium and the cysteine mole of the step (1) are respectively 2.5mmol, 1mmol
And 4mmol.
7. the preparation method of the metal sulfide catalyst of surface defect state modification according to claim 1, feature exist
In: nitrate is cadmium nitrate in the step (1).
8. according to claim 1 or the preparation method of the metal sulfide catalyst of 7 described in any item surface defect states modification,
It is characterized by: cadmium nitrate, nitric hydrate indium and the cysteine mole of the step (1) are respectively 0.5mmol, 1mmol
And 2mmol.
9. according to claim 1 or the preparation method of the catalyst of 7 described in any item surface defect state modifications, feature exist
In: cadmium nitrate, lanthanum nitrate and the cysteine mole of the step (1) are respectively 0.5mmol, 1mmol and 2mmol.
10. according to claim 1 or the preparation method of the catalyst of 7 described in any item surface defect state modifications, feature exist
In: cadmium nitrate, zinc nitrate and the cysteine mole of the step (1) are respectively 0.75mmol, 0.25mmol and 2mmol.
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