CN110433866A - A kind of Ni (OH)2Adulterate the composite photo-catalyst and the preparation method and application thereof of CdS - Google Patents
A kind of Ni (OH)2Adulterate the composite photo-catalyst and the preparation method and application thereof of CdS Download PDFInfo
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- CN110433866A CN110433866A CN201910742340.4A CN201910742340A CN110433866A CN 110433866 A CN110433866 A CN 110433866A CN 201910742340 A CN201910742340 A CN 201910742340A CN 110433866 A CN110433866 A CN 110433866A
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000013178 MIL-101(Cr) Substances 0.000 claims abstract description 149
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 43
- 239000001257 hydrogen Substances 0.000 claims abstract description 43
- 239000000470 constituent Substances 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 73
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 71
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 66
- 239000007788 liquid Substances 0.000 claims description 58
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 56
- 238000006243 chemical reaction Methods 0.000 claims description 46
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 39
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000006185 dispersion Substances 0.000 claims description 30
- 239000008367 deionised water Substances 0.000 claims description 28
- 229910021641 deionized water Inorganic materials 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 23
- 229910002651 NO3 Inorganic materials 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 23
- 239000002904 solvent Substances 0.000 claims description 17
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- NDBYHKKGKAWTJG-UHFFFAOYSA-N acetic acid;cadmium;dihydrate Chemical compound O.O.[Cd].CC(O)=O NDBYHKKGKAWTJG-UHFFFAOYSA-N 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 16
- 150000004690 nonahydrates Chemical class 0.000 claims description 14
- 238000000746 purification Methods 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 11
- 238000012545 processing Methods 0.000 claims description 8
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 claims description 7
- 238000002604 ultrasonography Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 239000011651 chromium Substances 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 235000010265 sodium sulphite Nutrition 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims 1
- ZSDJVGXBJDDOCD-UHFFFAOYSA-N benzene dioctyl benzene-1,2-dicarboxylate Chemical compound C(C=1C(C(=O)OCCCCCCCC)=CC=CC1)(=O)OCCCCCCCC.C1=CC=CC=C1 ZSDJVGXBJDDOCD-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 35
- 239000003054 catalyst Substances 0.000 abstract description 12
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000006641 stabilisation Effects 0.000 abstract description 3
- 238000011105 stabilization Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 44
- 229910052759 nickel Inorganic materials 0.000 description 32
- 238000004519 manufacturing process Methods 0.000 description 24
- 229960002050 hydrofluoric acid Drugs 0.000 description 18
- 238000000034 method Methods 0.000 description 9
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 8
- 238000001228 spectrum Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 5
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 229910002845 Pt–Ni Inorganic materials 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910052961 molybdenite Inorganic materials 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000003628 erosive effect Effects 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- KUCOHFSKRZZVRO-UHFFFAOYSA-N terephthalaldehyde Chemical compound O=CC1=CC=C(C=O)C=C1 KUCOHFSKRZZVRO-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- -1 ethyl alcohol Amine Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
-
- 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
-
- 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
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- 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
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- 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)
- Catalysts (AREA)
Abstract
The present invention relates to a kind of Ni (OH)2The composite photo-catalyst and the preparation method and application thereof for adulterating CdS, belongs to photocatalysis technology field.Ni (OH) of the present invention2The carrier for adulterating the composite photo-catalyst of CdS is Ni/MIL-101 (Cr) or MIL-101 (Cr), and active constituent is Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 0.1%~10.0%, CdS in Ni/MIL-101 (Cr) are doping Ni (OH) on 1%~20%, CdS2Quality be 0.1%~10.0%.The present invention uses Ni (OH)2Doping is carried on the CdS photochemical catalyst of Ni/MIL-101 (Cr) or MIL-101 (Cr), it is made effectively to avoid it that photoetch occurs, and guarantees that it produces the stabilization of hydrogen activity.
Description
Technical field
The present invention relates to a kind of Ni (OH)2The composite photo-catalyst and the preparation method and application thereof for adulterating CdS, belongs to light and urges
Change technical field.
Background technique
CdS photochemical catalyst is typical II-IV race direct band-gap semicondictor, and with range, larger and adjustable forbidden band is wide
Degree, excellent spectrochemical property and quantum efficiency are shown in visible region, is widely used in photocatalysis field, such as photocatalysis
Hydrogen manufacturing, carbon dioxide reduction, contaminant degradation etc..Compared to other semiconductor catalysts, CdS is suitble to band gap since it has
(2.4eV) and good electron charge transfer ability, and obtained extensive research.The H2-producing capacity of CdS material generally with
The structure of its own is related, wherein having the one-dimensional CdS nanometer rods compared with big L/D ratio, can show the list of electron-hole pair
To flowing and shorter surface transfer distance.Should theoretically have preferable H2-producing capacity.
But since CdS series photochemical catalyst in photocatalytic process is often accompanied by photoetch phenomenon, this makes CdS series light
Catalyst is difficult to be used widely in industrial circle.In order to effectively avoid the photoetch of CdS photochemical catalyst, which results in researchs
The extensive concern and interest of personnel.In recent years, many studies have shown that, it is rotten that CdS light can be effectively inhibited using reasonable strategy
Erosion, improves its stability.Often there are light deposition metal ion, nanosizing etc. to the method that CdS material is modified.Carry out
The CdS material of nanosizing can be contacted more fully with water due to its partial size very little, lead to mentioning for photocatalytic activity
It rises.Nearly 2 years, about use metal hydroxides or oxide to MoS2The report modified is commonplace: such as by Co3O4
Or Ni (OH)2With MoS2It is combined, is hindered according to the kinetic energy that the combination of report in this way can reduce the initial dissociation process of water
Hinder, alkali environment provides the active site of hydroxyl absorption, and the H* intermediate of generation can be by neighbouring MoS2Site absorption, favorably
In H* intermediate aggregation formation hydrogen.
One kind is described in the synthesis of CdS-Ni/MIL-101 (Cr) and Pt-Ni/CdS and its Photocatalyzed Hydrogen Production performance study
By CdS material load to the MIL-101 (Cr) mixed with Ni on method, to promoted material Photocatalyzed Hydrogen Production activity, still
Its production hydrogen activity is still lower, only 0.41mmol/ (gh).
Summary of the invention
For the low problem of prior art photochemical catalyst H2-producing capacity, the present invention provides a kind of Ni (OH)2Doping CdS's answers
Light combination catalyst and the preparation method and application thereof uses Ni (OH)2Doping is carried on Ni/MIL-101 (Cr) or MIL-101
(Cr) CdS photochemical catalyst makes it effectively avoid it that photoetch occurs, and guarantees that it produces the stabilization of hydrogen activity.
The present invention to solve above-mentioned technical problem and the technical solution adopted is that:
A kind of Ni (OH)2The composite photo-catalyst of CdS is adulterated, carrier is Ni/MIL-101 (Cr) or MIL-101 (Cr), is lived
Property ingredient be Ni (OH)2The CdS of doping, wherein the doping quality of Ni is 0.1%~10.0%, CdS in Ni/MIL-101 (Cr)
Load quality be 1%-20%, adulterate Ni (OH) on CdS2Quality be 0.1%-10.0%.
The Ni (OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) Ni/MIL-101 (Cr) or MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent,
Ultrasonic disperse handles 15~30min and obtains reaction system A；
(2) step (1) reaction system A is placed under the conditions of temperature is 180~200 DEG C and reacts 12~14h, be cooled to room
Temperature is separated by solid-liquid separation, dehydrated alcohol and acetone washing solid is respectively adopted, be dried in vacuo up to CdS@Ni/MIL-101 (Cr) or
CdS@MIL-101(Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) are added in NaOH solution and are mixed
It is even to obtain solution A, then by Ni (NO3)2Solution, which is added in solution A, obtains reaction system B, under room temperature, stirring condition, reactant
It is that B reacts 6~8h, is separated by solid-liquid separation, solid is successively washed using deionized water and dehydrated alcohol, be dried in vacuo up to Ni (OH)2/
CdS@Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) composite photo-catalyst.
The preparation method of the MIL-101 (Cr) is according to the document " synthesis of CdS-Ni/MIL-101 (Cr) and Pt-Ni/CdS
And its Photocatalyzed Hydrogen Production performance study " prepared；
The preparation method of the Ni/MIL-101 (Cr) is
Terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, Nickelous nitrate hexahydrate, ultrasound point are added
Dissipate processing, dropwise be added dropwise hydrofluoric acid and stir 30~40min obtain reaction system C, by reaction system C be placed in temperature be 150~
220 DEG C, 6~8h is reacted under stirring condition, be cooled to room temperature, purification process in DMF solvent be scattered in after washing using DMF, Gu
Liquid separation, is scattered in dehydrated alcohol after being washed using dehydrated alcohol and obtains dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A
Being placed in temperature is purification process 2 times under the conditions of 90~120 DEG C, then using being scattered in dehydrated alcohol and obtain after dehydrated alcohol washing
Dehydrated alcohol dispersion liquid B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 90~120 DEG C and are dried up to Ni/MIL-
101(Cr)。
Further, the terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio be 0.8~1.0g:2.3
~2.5g:30~50mL, the concentration of hydrofluoric acid are 0.05~0.51mol/L, and the volume ratio of deionized water and hydrofluoric acid is 100
The doping quality of Ni is 0.1%~10.0% in~500:1, Ni/MIL-101 (Cr).
The mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 2~10:1 in the step (1).
The concentration of NaOH solution is 0.1~1mol/L in the step (3), in solution A CdS@Ni/MIL-101 (Cr) or
The concentration of CdS@MIL-101 (Cr) is 0.01~0.02g/mL, Ni (NO3)2The concentration of solution is 0.05~0.1mol/L, Ni
(NO3)2Ni (NO in solution3)2Mass ratio with CdS in CdS@Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) is (0.1
~10.0): 100.
The Ni (OH)2Adulterate application of the composite photo-catalyst of CdS in photochemical catalyzing hydrogen making.
Further, the sacrifice agent of the light-catalyzed reaction is sodium sulfite/vulcanized sodium system, methanol system, three ethyl alcohol
Amine system or lactic acid system, the solvent of light-catalyzed reaction are pure water or ultrapure water, and the temperature of light-catalyzed reaction is 2~20 DEG C,
PH value is 5~9, Ni (OH)2The usage amount for adulterating the composite photo-catalyst of CdS is 0.1~0.5g/L.
A kind of Ni (OH) of light deposition Pt2The composite photo-catalyst for adulterating CdS, at Ni (OH)2The complex light of doping CdS is urged
Agent surface light deposition Pt.
Beneficial effects of the present invention:
(1) direct band gap of CdS is wide, but specific surface area is low, and is easy to happen photoetch under illumination condition, so
Its Photocatalyzed Hydrogen Production activity is lower, and the present invention passes through Ni (OH)2Doping be modified and load to Ni/MIL-101 (Cr) or
It on MIL-101 (Cr), can effectively avoid it that photoetch occurs, guarantee that it produces the stabilization of hydrogen activity, to improve its reality
Application value；
(2) Ni (OH) of the present invention2The production hydrogen activity for the CdS material of doping loaded on Ni/MIL-101 (Cr) reaches
22.20mmol/ (gh), photocatalysis good cycling stability.
Detailed description of the invention
Fig. 1 is CdS, Ni/MIL-101 (Cr) and Ni (OH) of embodiment 12The XRD of/CdS@Ni/MIL-101 (Cr) is composed
Figure；
Fig. 2 is the Ni (OH) of embodiment 22The UV, visible light of/CdS Ni/MIL-101 (Cr) material and other materials is unrestrained anti-
Penetrate spectrogram；
Fig. 3 is the Ni (OH) of embodiment 22The SEM figure (a) and energy spectrum diagram (b, c) of/CdS@Ni/MIL-101 (Cr) material；
Fig. 4 is the Ni (OH) of embodiment 22The characteristic spectrum of the XPS full spectrogram (a) and Ni 2p of/CdS@Ni/MIL-101 (Cr)
Scheme the feature spectrogram (c) of (b), O 1s；
Fig. 5 is 0.5% Ni of control group NaOH/10%CdS@5%Ni/MIL-101 (Cr), pure CdS and embodiment 2
(OH)2The Photocatalyzed Hydrogen Production activity figure of/10%CdS@5%Ni/MIL-101 (Cr)；
Fig. 6 is Ni (OH)2Doping to Ni (OH)2The Photocatalyzed Hydrogen Production of/CdS@Ni/MIL-101 (Cr) material is active
It influences；
Fig. 7 is the Ni (OH) of embodiment 32The photocatalysis cyclical stability of/CdS@Ni/MIL-101 (Cr) material.
Specific embodiment:
With reference to embodiment, the invention will be further described.
A kind of embodiment 1: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 10%, CdS2Quality be 1%；
Ni(OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, add Nickelous nitrate hexahydrate, ultrasound
Hydrofluoric acid is added dropwise dropwise and stirs 30min and obtains reaction system C for decentralized processing, by reaction system C be placed in temperature be 150 DEG C,
6h is reacted under stirring condition, is cooled to room temperature, purification process in DMF solvent is scattered in after washing using DMF, is separated by solid-liquid separation, adopts
It is scattered in after being washed with dehydrated alcohol in dehydrated alcohol and obtains dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A is placed in temperature and is
Purification process 2 times under the conditions of 90 DEG C, then dehydrated alcohol dispersion liquid is obtained using being scattered in dehydrated alcohol after dehydrated alcohol washing
B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 90 DEG C and are dried up to Ni/MIL-101 (Cr)；Further, institute
State terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio be 0.8g:2.5g:30mL, the concentration of hydrofluoric acid is
The volume ratio of 0.51mol/L, deionized water and hydrofluoric acid is 100:1, and the doping quality of Ni is 5% in Ni/MIL-101 (Cr)；
Ni/MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasonic disperse handles 15min
Obtain reaction system A；Wherein the mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 10:1；
(2) step (1) reaction system A is placed under the conditions of temperature is 150 DEG C and reacts 12h, be cooled to room temperature, solid-liquid point
From dehydrated alcohol and acetone washing solid is respectively adopted, is dried in vacuo up to CdS@Ni/MIL-101 (Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) is added to be uniformly mixed in NaOH solution and obtains solution A, then will
Ni(NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B reacts 6h, solid-liquid point
From successively washing solid using deionized water and dehydrated alcohol, be dried in vacuo up to Ni (OH)2/CdS@Ni/MIL-101(Cr)
Composite photo-catalyst；Wherein the concentration of NaOH solution is 0.5mol/L, and the concentration of CdS@Ni/MIL-101 (Cr) is in solution A
0.0125g/mL, Ni (NO3)2The concentration of solution is 0.05mol/L, Ni (NO3)2Ni (NO in solution3)2With CdS@Ni/MIL-101
(Cr) mass ratio of CdS is 1:100 in；
The present embodiment CdS, Ni/MIL-101 (Cr) and Ni (OH)2The XRD spectra of/CdS@Ni/MIL-101 (Cr) is shown in Fig. 1,
From fig. 1, it can be seen that peak position and the peak intensity out of material manufactured in the present embodiment and standard items are consistent substantially, illustrate its crystalline form
Structure and standard items are reported intimate consistent, and Ni (OH) has been loaded2Material in Ni/MIL-101 (Cr) material peak type with it is pure
The peak type of Ni/MIL-101 (Cr) material is substantially similar；Since the load capacity of CdS is lower, Ni (OH)2/CdS@ Ni/MIL-101
(Cr) characteristic peak of CdS is weaker in material, but is still able to find out and is equipped with the diffraction of apparent CdS crystal face in 26.5 ° of equipotentials
Peak, and wherein there is no the appearance of the diffraction maximum of other crystal phases, so according to XRD spectra, it can be determined that go out synthesis really
The CdS-loaded composite material on Ni/MIL-101 (Cr).
A kind of embodiment 2: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 10%, CdS2Quality be 0.5%；
Ni(OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, add Nickelous nitrate hexahydrate, ultrasound
Hydrofluoric acid is added dropwise dropwise and stirs 30min and obtains reaction system C for decentralized processing, by reaction system C be placed in temperature be 180 DEG C,
6h is reacted under stirring condition, is cooled to room temperature, purification process in DMF solvent is scattered in after washing using DMF, is separated by solid-liquid separation, adopts
It is scattered in after being washed with dehydrated alcohol in dehydrated alcohol and obtains dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A is placed in temperature and is
Purification process 2 times under the conditions of 90 DEG C, then dehydrated alcohol dispersion liquid is obtained using being scattered in dehydrated alcohol after dehydrated alcohol washing
B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 90 DEG C and are dried up to Ni/MIL-101 (Cr)；Wherein terephthaldehyde
Acid, Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio 0.8g:2.5g:30mL, the concentration of hydrofluoric acid is 0.05mol/L, deionization
The volume ratio of water and hydrofluoric acid is 100:1, and the doping quality of Ni is 5% in Ni/MIL-101 (Cr)；
Ni/MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasonic disperse handles 20min
Obtain reaction system A；Wherein the mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 2:1；
(2) step (1) reaction system A is placed under the conditions of temperature is 180 DEG C and reacts 12h, be cooled to room temperature, solid-liquid point
From dehydrated alcohol and acetone washing solid is respectively adopted, is dried in vacuo up to CdS@Ni/MIL-101 (Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) is added to be uniformly mixed in NaOH solution and obtains solution A, then will
Ni(NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B reacts h, solid-liquid point
From successively washing solid using deionized water and dehydrated alcohol, be dried in vacuo up to Ni (OH)2/CdS@Ni/MIL-101(Cr)
Composite photo-catalyst；Wherein the concentration of NaOH solution is 0.5mol/L, and the concentration of CdS@Ni/MIL-101 (Cr) is in solution A
0.0125g/mL, Ni (NO3)2The concentration of solution is 0.05mol/L, Ni (NO3)2Ni (NO in solution3)2With CdS@Ni/MIL-101
(Cr) mass ratio of CdS is 0.5:100 in；
The present embodiment 0.5%Ni (OH)2/ 10%CdS@5%Ni/MIL-101 (Cr) and pure CdS and carrier 5%Ni/
UV-vis DRS spectrogram of MIL-101 (Cr) material in 200-800nm is shown in Fig. 2, as can be seen from Figure 2, in visible region, 5%
Ni/MIL-101 (Cr) material has light certain absorbability, and has loaded doping Ni (OH) on it2CdS material
Later, composite material further promotes the absorbability of light, and is significantly higher than solvent-thermal method under identical conditions and prepares
Pure CdS material for light absorbability；And in ultraviolet region, 0.5%Ni (OH)2/ 10%CdS@5%Ni/MIL-101
(Cr) material obviously weakens the absorbability of light, and deduction may be remained since its MIL-101 (Cr) structure suffers erosion
Result in its reduction for light absorpting ability；But pass through Ni (OH)2Suction of the CdS material of doping in visible region for light
The enhancing of receipts ability, being analyzed this may be one of the reason of its in subsequent production hydrogen experiment produces hydrogen activity enhancing；
The present embodiment 0.5%Ni (OH)2The SEM figure (a) and energy spectrum diagram (b, c) of/CdS@Ni/MIL-101 (Cr) material is shown in
Fig. 3, power spectrum are that scanning electron microscope or transmission electron microscope is cooperated to be used to analyze the element species and content of material domain,
Principle is the characteristic x-ray wavelength that oneself is all had due to various elements, and the characteristic energy released during energy level transition
△ E determines the size of characteristic wavelength；From Fig. 3 (a) 0.5%Ni (OH)2The scanning electricity of/CdS@Ni/MIL-101 (Cr) material
Mirror image is analyzed by UV-vis DRS early period, and Ni/MIL-101 (Cr) structure of material is likely to be broken, by SEM
Analysis is difficult to see the octahedral structure of Ni/MIL-101 (Cr) feature, but has more column structure, and CdS is substantially presented
Spherical shape loads thereon；The electro microscope energy spectrum figure of different location is shown in figure (b, c), since the analysis of EDS is random selected analysis position,
So the analysis of spectra of the different location of material has a degree of difference；It is analyzed due to electro microscope energy spectrum and needs with silicon wafer to be to carry
Body, so occurring the photon detection peak of apparent Si in two parts of spectrograms；S, the peak of Cd and Cr has confirmed main body in material
The element of frame forms, and the appearance at the peak Ni confirms Ni (OH)2Success is adulterated；
The present embodiment 0.5%Ni (OH)2The characteristic spectrum of the XPS full spectrogram and Ni, O of/CdS@Ni/MIL-101 (Cr) material
Figure is shown in Fig. 4, and when test, the peak position that goes out of the C 1s for correction is 285.5eV, deviates from 0.7 than standard school peak 284.8eV
eV；With reference to the accompanying drawings 4 (b), there is apparent appearance situation near 855.4eV and 873.4eV, which meets the position at the peak Ni 2p
It sets and corresponds to Ni (OH)2In Ni, be located in attached drawing 4 (c) peak of the O 1s at 530.1eV also with Ni (OH)2In O it is corresponding,
Thereby confirm Ni (OH)2Presence；And the peak Na 1s may be due to excessive NaOH do not cleaned completely it is remaining.
A kind of embodiment 3: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 10%, CdS2Quality be 0.1%；
The present embodiment Ni (OH)2The preparation method of the composite photo-catalyst of doping CdS is almost the same with embodiment 1, no
It is with place: Ni (NO3)2Ni (NO in solution3)2Mass ratio with CdS in CdS@Ni/MIL-101 (Cr) is 0.1:100.
A kind of embodiment 4: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 10%, CdS2Quality be 0.2%；
The present embodiment Ni (OH)2The preparation method of the composite photo-catalyst of doping CdS is almost the same with embodiment 1, no
It is with place: Ni (NO3)2Ni (NO in solution3)2Mass ratio with CdS in CdS@Ni/MIL-101 (Cr) is 0.2:100.
A kind of embodiment 5: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 10%, CdS2Quality be 2%；
The present embodiment Ni (OH)2The preparation method of the composite photo-catalyst of doping CdS is almost the same with embodiment 1, no
It is with place: Ni (NO3)2Ni (NO in solution3)2Mass ratio with CdS in CdS@Ni/MIL-101 (Cr) is 2:100；
Ni(OH)2Adulterate the measurement of the production hydrogen activity of CdS@Ni/MIL-101 (Cr) series material: cold using 10 DEG C of circulations
Condensate, 300W xenon lamp use the Na of 0.05mol for simulating all band sunlight2S/Na2SO3System is urged as sacrifice agent, light
The dosage of agent is 20mg, and experiment carries out 4h；
Ni (NO is not added according to the method preparation of embodiment 13)2Composite material as a control group, be denoted as NaOH/
10%CdS@5%Ni/MIL-101 (Cr)；
0.5% Ni (OH) of control group NaOH/10%CdS@5%Ni/MIL-101 (Cr), pure CdS and embodiment 22/
The Photocatalyzed Hydrogen Production activity figure of 10%CdS@5%Ni/MIL-101 (Cr) is shown in Fig. 5, as can be seen from Figure 5, does not carry out Ni (OH)2Load
And only under same strong alkali environment by dipping NaOH/10%CdS@5%Ni/MIL-101 (Cr) sample hydrogen output with
Pure CdS is not much different, and embodiment 2 has carried out Ni (OH)2The hydrogen output of the sample of load is much higher by both remaining, to demonstrate,prove
Real Ni (OH)2Load can effectively act synergistically really with catalyst, the effective photocatalytic activity for promoting catalyst,
And only by the dipping of strong alkali environment, there is no methods to reach this effect；
Control group NaOH/10%CdS@5%Ni/MIL-101 (Cr) and Examples 1 to 5 Ni (OH)2/CdS@Ni/MIL-
The comparison diagram of 101 (Cr) materials is shown in Fig. 6, as can be seen from Figure 6, different Ni (OH)2The Ni (OH) of doping2/CdS@Ni/MIL-101
(Cr) material has shown good photocatalytic activity, and the production hydrogen than pure CdS after the experiment of the production hydrogen of 4h
It is active high；Ni(OH)2The production hydrogen activity of/CdS@Ni/MIL-101 (Cr) material is about Ni (OH)2Doping show and first increase
The trend reduced afterwards, wherein as Ni (OH)2Doping be 0.5% when, the production hydrogen activity of material is best, has reached 22.20
Mmol/ (gh) is pure CdS produces hydrogen activity under identical conditions 4.13 times；And works as and Ni (OH) is gradually increased2Doping extremely
When 1.0%, the production hydrogen activity of material is slowly drop down to 21.33mmol/ (gh), i.e., as Ni (OH)2Doping be 0.5% or
When 1.0%, produces hydrogen activity and be not much different, but work as Ni (OH)2Doping continue improve when material production hydrogen activity substantially
Decline；
With embodiment 3Ni (OH)2Doping be 0.1% 0.1%Ni (OH)2/ 10%CdS@5%Ni/MIL-101
(Cr) circulation experiment is carried out, each production hydrogen process continues 4h, and cycle performance figure is shown in Fig. 7, recycles in 3 Photocatalyzed Hydrogen Productions real
In testing, the 2nd time and the 3rd time experimental data is obviously better than the 1st experimental data, this is because the light of semiconductor material swashs
Effect living is so that the production hydrogen activity of material is further promoted, and then experimental data is kept substantially and unanimously also illustrates twice
The cyclical stability of the material is preferable.
Embodiment 6: light deposition, which refers to, carries out illumination to semiconductor grain in the aqueous phase solution of metal salt, can frequently result in
The phenomenon that semiconductor surface deposits well-defined metal (oxide) nano particle；With embodiment 3Ni (OH)2Doping
For 0.1% 0.1%Ni (OH)2/ 10%CdS@5%Ni/MIL-101 (Cr) carries out the experiment of light deposition Pt, by 0.1% Ni
(OH)2/ 10%CdS@5%Ni/MIL-101 (Cr) is added in the ultrapure water in Photoreactor and is uniformly dispersed to obtain dispersion
It is 0.1%Ni (OH) in dispersion2The concentration of/10%CdS@5%Ni/MIL-101 (Cr) is 0.0125g/mL；It is added
H2PtCl6, H2PtCl6Additional amount be 0.04375mg/mL, stirring, simulated solar irradiation under the conditions of carry out light deposition reaction
4h obtains the 0.1%Ni (OH) of light deposition Pt2/ CdS@Ni/MIL-101 (Cr) material；The photocatalysis of material before and after light deposition Pt
It is as shown in table 1 to produce hydrogen activity,
Table 1: 0.1%Ni (OH) before and after light deposition Pt2The Photocatalyzed Hydrogen Production activity of/CdS@Ni/MIL-101 (Cr) material is right
Than
As known from Table 1, the production hydrogen activity for having carried out the material of light deposition has reached 56.97mmol/ (gh), is light deposition
4.33 times before Pt, which is more than about 2.53 times of current paper report value of current CdS series material.
A kind of embodiment 7: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 10%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 0.1%, CdS2Quality be 10%；
Ni(OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, add Nickelous nitrate hexahydrate, ultrasound
Hydrofluoric acid is added dropwise dropwise and stirs 30min and obtains reaction system C for decentralized processing, by reaction system C be placed in temperature be 150 DEG C,
6h is reacted under stirring condition, is cooled to room temperature, purification process in DMF solvent is scattered in after washing using DMF, is separated by solid-liquid separation, adopts
It is scattered in after being washed with dehydrated alcohol in dehydrated alcohol and obtains dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A is placed in temperature and is
Purification process 2 times under the conditions of 90 DEG C, then dehydrated alcohol dispersion liquid is obtained using being scattered in dehydrated alcohol after dehydrated alcohol washing
B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 90 DEG C and are dried up to Ni/MIL-101 (Cr)；Wherein terephthaldehyde
Acid, Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio g:g:mL be 0.8:2.3:30, the concentration of hydrofluoric acid is 0.05mol/L, hydrogen
The volume ratio of fluoric acid and deionized water is 1:100, and the doping quality of Ni is 0.1% in Ni/MIL-101 (Cr)；
Ni/MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasonic disperse handles 15min
Obtain reaction system A；Wherein the mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 10:1；
(2) step (1) reaction system A is placed under the conditions of temperature is 180 DEG C and reacts 12h, be cooled to room temperature, solid-liquid point
From dehydrated alcohol and acetone washing solid is respectively adopted, is dried in vacuo up to CdS@Ni/MIL-101 (Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) is added to be uniformly mixed in NaOH solution and obtains solution A, then will
Ni(NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B reacts 6h, solid-liquid point
From successively washing solid using deionized water and dehydrated alcohol, be dried in vacuo up to Ni (OH)2/CdS@Ni/MIL-101(Cr)
Composite photo-catalyst；Wherein the concentration of NaOH solution is 0.1mol/L, and the concentration of CdS@Ni/MIL-101 (Cr) is in solution A
0.01g/mL, Ni (NO3)2The concentration of solution is 0.05mol/L, Ni (NO3)2Ni (NO in solution3)2With CdS@Ni/MIL-101
(Cr) mass ratio of CdS is 10:100 in；
The present embodiment Ni (OH)2It is 13.17mmol/ (gh) that the composite photo-catalyst for adulterating CdS, which produces hydrogen activity,.
A kind of embodiment 8: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 0.5%, CdS2Quality be 0.5%；
Ni(OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, add Nickelous nitrate hexahydrate, ultrasound
Hydrofluoric acid is added dropwise dropwise and stirs 35min and obtains reaction system C for decentralized processing, by reaction system C be placed in temperature be 180 DEG C,
7h is reacted under stirring condition, is cooled to room temperature, purification process in DMF solvent is scattered in after washing using DMF, is separated by solid-liquid separation, adopts
It is scattered in after being washed with dehydrated alcohol in dehydrated alcohol and obtains dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A is placed in temperature and is
Purification process 2 times under the conditions of 110 DEG C, then dehydrated alcohol dispersion liquid is obtained using being scattered in dehydrated alcohol after dehydrated alcohol washing
B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 110 DEG C and are dried up to Ni/MIL-101 (Cr)；Wherein to benzene two
Formic acid, Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio g:g:mL be 5:2.4:40, the concentration of hydrofluoric acid is 0.30mol/L, hydrogen
The volume ratio of fluoric acid and deionized water is 300:100, and the doping quality of Ni is 5% in Ni/MIL-101 (Cr)；
Ni/MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasonic disperse handles 20min
Obtain reaction system A；Wherein the mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 5:1；
(2) step (1) reaction system A is placed under the conditions of temperature is 190 DEG C and reacts 13h, be cooled to room temperature, solid-liquid point
From dehydrated alcohol and acetone washing solid is respectively adopted, is dried in vacuo up to CdS@Ni/MIL-101 (Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) is added to be uniformly mixed in NaOH solution and obtains solution A, then will
Ni(NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B reacts 7h, solid-liquid point
From successively washing solid using deionized water and dehydrated alcohol, be dried in vacuo up to Ni (OH)2/CdS@Ni/MIL-101(Cr)
Composite photo-catalyst；Wherein the concentration of NaOH solution is 0.5mol/L, and the concentration of CdS@Ni/MIL-101 (Cr) is in solution A
0.3g/mL, Ni (NO3)2The concentration of solution is 0.05mol/L, Ni (NO3)2Ni (NO in solution3)2With CdS@Ni/MIL-101
(Cr) mass ratio of CdS is 0.5:100 in；
The present embodiment Ni (OH)2It is 22.20mmol/ (gh) that the composite photo-catalyst for adulterating CdS, which produces hydrogen activity,.
A kind of embodiment 9: Ni (OH)2Adulterate CdS composite photo-catalyst, carrier be Ni/MIL-101 (Cr), activity at
It is divided into Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 10%, CdS in Ni/MIL-101 (Cr) are
Ni (OH) is adulterated on 0.1%, CdS2Quality be 10%；
Ni(OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, add Nickelous nitrate hexahydrate, ultrasound
Hydrofluoric acid is added dropwise dropwise and stirs 40min and obtains reaction system C for decentralized processing, by reaction system C be placed in temperature be 220 DEG C,
8h is reacted under stirring condition, is cooled to room temperature, purification process in DMF solvent is scattered in after washing using DMF, is separated by solid-liquid separation, adopts
It is scattered in after being washed with dehydrated alcohol in dehydrated alcohol and obtains dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A is placed in temperature and is
Purification process 2 times under the conditions of 120 DEG C, then dehydrated alcohol dispersion liquid is obtained using being scattered in dehydrated alcohol after dehydrated alcohol washing
B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 120 DEG C and are dried up to Ni/MIL-101 (Cr)；Wherein to benzene two
Formic acid, Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio g:g:mL be 1:2.5:50, the concentration of hydrofluoric acid is 0.51mol/L, hydrogen
The volume ratio of fluoric acid and deionized water is 1:500, and the doping quality of Ni is 10% in Ni/MIL-101 (Cr)；
Ni/MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasonic disperse handles 30min
Obtain reaction system A；Wherein the mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 2:1；
(2) step (1) reaction system A is placed under the conditions of temperature is 200 DEG C and reacts 14h, be cooled to room temperature, solid-liquid point
From dehydrated alcohol and acetone washing solid is respectively adopted, is dried in vacuo up to CdS@Ni/MIL-101 (Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) is added to be uniformly mixed in NaOH solution and obtains solution A, then will
Ni(NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B reacts 8h, solid-liquid point
From successively washing solid using deionized water and dehydrated alcohol, be dried in vacuo up to Ni (OH)2/CdS@Ni/MIL-101(Cr)
Composite photo-catalyst；Wherein the concentration of NaOH solution is 1mol/L, and the concentration of CdS@Ni/MIL-101 (Cr) is in solution A
0.02g/mL, Ni (NO3)2The concentration of solution is 0.1mol/L, Ni (NO3)2Ni (NO in solution3)2With CdS@Ni/MIL-101
(Cr) mass ratio of CdS is 10:100 in；
The present embodiment Ni (OH)2It is 18.60mmol/ (gh) that the composite photo-catalyst for adulterating CdS, which produces hydrogen activity,.
A kind of embodiment 10: Ni (OH)2The composite photo-catalyst of CdS is adulterated, carrier is MIL-101 (Cr), active constituent
For Ni (OH)2The CdS of doping, the load quality that wherein the doping quality of Ni is 5%, CdS in Ni/MIL-101 (Cr) is 5%,
Ni (OH) is adulterated on CdS2Quality be 5%；
Ni(OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, the specific steps are as follows:
(1) it is made according to " synthesis of CdS-Ni/MIL-101 (Cr) and Pt-Ni/CdS and its Photocatalyzed Hydrogen Production performance study "
Standby MIL-101 (Cr)；
MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasonic disperse processing 30min is obtained
To reaction system A；Wherein the mass ratio of MIL-101 (Cr) and acetic acid dihydrate cadmium is 5:1；
(2) step (1) reaction system A is placed under the conditions of temperature is 190 DEG C and reacts 13h, be cooled to room temperature, solid-liquid point
From dehydrated alcohol and acetone washing solid is respectively adopted, is dried in vacuo up to CdS@MIL-101 (Cr)；
(3) step (2) CdS@MIL-101 (Cr) is added to be uniformly mixed in NaOH solution and obtains solution A, then by Ni
(NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B reacts 7h, is separated by solid-liquid separation,
Solid is successively washed using deionized water and dehydrated alcohol, is dried in vacuo up to Ni (OH)2/ CdS@MIL-101 (Cr) complex light
Catalyst；Wherein the concentration of NaOH solution is 0.3mol/L, and the concentration of CdS@MIL-101 (Cr) is 0.5g/mL, Ni in solution A
(NO3)2The concentration of solution is 0.05mol/L, Ni (NO3)2Ni (NO in solution3)2With the quality of CdS in CdS@MIL-101 (Cr)
Than for 5:100；
The present embodiment Ni (OH)2It is 12.33mmol/ (gh) that the composite photo-catalyst for adulterating CdS, which produces hydrogen activity,.
Specific embodiments of the present invention are explained in detail above in conjunction with attached drawing, but the present invention is not limited to above-mentioned realities
Example is applied, it within the knowledge of a person skilled in the art, can also be without departing from the purpose of the present invention
Various changes can be made.
Claims (9)
1. a kind of Ni (OH)2Adulterate the composite photo-catalyst of CdS, it is characterised in that: carrier is Ni/MIL-101 (Cr) or MIL-
101 (Cr), active constituent are Ni (OH)2The CdS of doping, wherein in Ni/MIL-101 (Cr) Ni doping quality be 0.1%~
The load quality of 10.0%, CdS are to adulterate Ni (OH) on 1%~20%, CdS2Quality be 0.1%~10.0%.
2. Ni described in claim 1 (OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, which is characterized in that specific steps
It is as follows:
(1) Ni/MIL-101 (Cr) or MIL-101 (Cr), acetic acid dihydrate cadmium are added in dimethyl sulfoxide solvent, ultrasound
15~30min of decentralized processing obtains reaction system A；
(2) step (1) reaction system A is placed under the conditions of temperature is 180~200 DEG C and reacts 12~14h, be cooled to room temperature, Gu
Liquid separation, is respectively adopted dehydrated alcohol and acetone washing solid, is dried in vacuo up to CdS@Ni/MIL-101 (Cr) or CdS@
MIL-101(Cr)；
(3) step (2) CdS@Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) are added in NaOH solution and are uniformly mixed
To solution A, then by Ni (NO3)2Solution, which is added in solution A, obtains reaction system B, and under room temperature, stirring condition, reaction system B is anti-
6~8h is answered, is separated by solid-liquid separation, solid is successively washed using deionized water and dehydrated alcohol, is dried in vacuo up to Ni (OH)2/CdS@
Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) composite photo-catalyst.
3. Ni (OH) according to claim 22Adulterate the preparation method of the composite photo-catalyst of CdS, it is characterised in that: Ni/
The preparation method of MIL-101 (Cr) is
Terephthalic acid (TPA), Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water are uniformly dispersed, add Nickelous nitrate hexahydrate, at ultrasonic disperse
Reason, is added dropwise hydrofluoric acid dropwise and 30~40min of stirring obtains reaction system C, and it is 150~220 that reaction system C, which is placed in temperature,
DEG C, 6~8h is reacted under stirring condition, be cooled to room temperature, purification process in DMF solvent, solid-liquid point be scattered in after washing using DMF
From being scattered in after being washed using dehydrated alcohol in dehydrated alcohol and obtain dehydrated alcohol dispersion liquid A, dehydrated alcohol dispersion liquid A is placed in
Temperature be 90~120 DEG C under the conditions of purification process 2 times, then using dehydrated alcohol washing after be scattered in dehydrated alcohol obtain it is anhydrous
Alcohol dispersion liquid B, dehydrated alcohol dispersion liquid B are placed under the conditions of temperature is 90~120 DEG C and are dried up to Ni/MIL-101
(Cr)。
4. Ni (OH) according to claim 32Adulterate the preparation method of the composite photo-catalyst of CdS, it is characterised in that: to benzene
Dioctyl phthalate, Chromium nitrate (Cr(NO3)3),nonahydrate, deionized water solid-to-liquid ratio be 0.8~1.0g:2.3~2.5g:30~50mL, hydrofluoric acid it is dense
Spending is 0.05~0.51mol/L, and the volume ratio of deionized water and hydrofluoric acid is 100~500:1, Ni in Ni/MIL-101 (Cr)
Adulterating quality is 0.1%~10.0%.
5. the Ni according to Claims 2 or 3 (OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, it is characterised in that: step
Suddenly the mass ratio of Ni/MIL-101 (Cr) and acetic acid dihydrate cadmium is 2~10:1 in (1).
6. the Ni according to Claims 2 or 3 (OH)2Adulterate the preparation method of the composite photo-catalyst of CdS, it is characterised in that: step
Suddenly the concentration of NaOH solution is 0.1~1mol/L, CdS@Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) in solution A in (3)
Concentration be 0.01~0.02g/mL, Ni (NO3)2The concentration of solution is 0.05~0.1mol/L, Ni (NO3)2Ni in solution
(NO3)2Mass ratio with CdS in CdS@Ni/MIL-101 (Cr) or CdS@MIL-101 (Cr) is (0.1~10.0): 100.
7. Ni described in claim 1 (OH)2Adulterate application of the composite photo-catalyst of CdS in photochemical catalyzing hydrogen making.
8. applying according to claim 7, it is characterised in that: the sacrifice agent of light-catalyzed reaction is sodium sulfite/vulcanized sodium body
System, methanol system, triethanolamine system or lactic acid system, the solvent of light-catalyzed reaction are pure water or ultrapure water, light-catalyzed reaction
Temperature be 2~20 DEG C, pH value be 5~9, Ni (OH)2The usage amount for adulterating the composite photo-catalyst of CdS is 0.1~0.5g/
L。
9. the Ni (OH) of light deposition Pt a kind of2Adulterate the composite photo-catalyst of CdS, it is characterised in that: in the Ni of claim 1
(OH)2Adulterate the composite photo-catalyst surface light deposition Pt of CdS.
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