CN113289645B - One-dimensional self-assembled composite photocatalyst, preparation method and application thereof - Google Patents
One-dimensional self-assembled composite photocatalyst, preparation method and application thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 63
- 239000002131 composite material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000011701 zinc Substances 0.000 claims abstract description 62
- 239000011669 selenium Substances 0.000 claims abstract description 58
- 238000003756 stirring Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- PFNQVRZLDWYSCW-UHFFFAOYSA-N (fluoren-9-ylideneamino) n-naphthalen-1-ylcarbamate Chemical compound C12=CC=CC=C2C2=CC=CC=C2C1=NOC(=O)NC1=CC=CC2=CC=CC=C12 PFNQVRZLDWYSCW-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000001412 amines Chemical class 0.000 claims abstract description 16
- 239000012046 mixed solvent Substances 0.000 claims abstract description 16
- 239000002086 nanomaterial Substances 0.000 claims abstract description 14
- 239000002135 nanosheet Substances 0.000 claims abstract description 14
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- XNVJGKKANSYGKB-UHFFFAOYSA-N [Zn].[Se].[Cd] Chemical compound [Zn].[Se].[Cd] XNVJGKKANSYGKB-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000004321 preservation Methods 0.000 claims abstract description 9
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 7
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229960001471 sodium selenite Drugs 0.000 claims abstract description 6
- 239000011781 sodium selenite Substances 0.000 claims abstract description 6
- 235000015921 sodium selenite Nutrition 0.000 claims abstract description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 239000010949 copper Substances 0.000 claims description 34
- 238000001338 self-assembly Methods 0.000 claims description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 239000002244 precipitate Substances 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 14
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- 238000006722 reduction reaction Methods 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical group [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 5
- 229920001223 polyethylene glycol Polymers 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 3
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 2
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical group [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 2
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 2
- 230000001678 irradiating effect Effects 0.000 claims description 2
- 230000003287 optical effect Effects 0.000 claims description 2
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960001124 trientine Drugs 0.000 claims 2
- 239000000203 mixture Substances 0.000 description 10
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 7
- 229910002091 carbon monoxide Inorganic materials 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000031700 light absorption Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SRKRSWKCLVMJRZ-UHFFFAOYSA-N [S-2].S.[SeH2].[Cd+2] Chemical compound [S-2].S.[SeH2].[Cd+2] SRKRSWKCLVMJRZ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- UQMZPFKLYHOJDL-UHFFFAOYSA-N zinc;cadmium(2+);disulfide Chemical compound [S-2].[S-2].[Zn+2].[Cd+2] UQMZPFKLYHOJDL-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J27/057—Selenium or tellurium; Compounds thereof
- B01J27/0573—Selenium; Compounds thereof
-
- 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
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/40—Carbon monoxide
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- Chemical Kinetics & Catalysis (AREA)
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- Thermal Sciences (AREA)
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Abstract
本发明公开了一种一维自组装ZnxCd1‑xSe/Cu2O@Cu复合光催化剂及其制备方法和应用。本发明一维自组装ZnxCd1‑xSe光催化剂的制备方法包括：(1)将锌源和亚硒酸钠在水‑有机胺‑水合肼三元混合溶剂中溶解并搅拌均匀，升温，保温反应，获得硒化锌纳米片；(2)将硒化锌纳米片溶解于水‑有机胺二元混合溶剂中，加入镉源，搅拌，升温，保温反应获得硒镉锌纳米结构即为一维自组装ZnxCd1‑xSe光催化剂；(3)将Cu2O@Cu分散于二次水中，超声分散，加入硒镉锌纳米结构，得一维自组装ZnxCd1‑xSe/Cu2O@Cu复合光催化剂。本发明的制备方法反应设备简单，容易操作，成本低，反应条件温和，所得光催化剂产品的分散性好，光催化性活性高，光催化稳定较好，具有较好的应用前景。
The invention discloses a one-dimensional self-assembled Zn x Cd 1-x Se/Cu 2 O@Cu composite photocatalyst and a preparation method and application thereof. The preparation method of the one-dimensional self-assembled Zn x Cd 1-x Se photocatalyst of the present invention includes: (1) dissolving zinc source and sodium selenite in a water-organic amine-hydrazine hydrate ternary mixed solvent, stirring evenly, heating up , heat preservation reaction to obtain zinc selenide nanosheets; (2) dissolving zinc selenide nanosheets in a water-organic amine binary mixed solvent, adding a cadmium source, stirring, heating, and heat preservation reaction to obtain selenium cadmium zinc nanostructures: One-dimensional self-assembled Zn x Cd 1‑x Se photocatalyst; (3) Disperse Cu 2 O@Cu in secondary water, ultrasonically disperse, and add selenium-cadmium-zinc nanostructures to obtain one-dimensional self-assembled Zn x Cd 1‑x Se/Cu 2 O@Cu composite photocatalyst. The preparation method of the invention has simple reaction equipment, easy operation, low cost, mild reaction conditions, good dispersibility of the obtained photocatalyst product, high photocatalytic activity, good photocatalytic stability and good application prospect.
Description
Technical Field
The invention relates to the technical field of catalyst synthesis, in particular to a one-dimensional self-assembly composite photocatalyst, and a preparation method and application thereof, and more particularly relates to one-dimensional self-assembly ZnxCd1-xSe/Cu2O @ Cu composite photocatalyst and preparation method and application thereof.
Background
While the social economy is rapidly developed, the natural environment pollution and the energy exhaustion threaten the health, survival and development of human beings. As fossil fuels are continuously developed and the amount of carbon dioxide emissions increases year by year, human life faces a great threat, and one of the ways to reduce this threat is to convert carbon dioxide.
The traditional method for converting carbon dioxide adopts hydrogen catalytic reduction at high temperature to produce products such as carbon monoxide, methane, methanol and the like, and has high energy consumption. The photoelectrocatalysis can realize the reduction of carbon dioxide under a mild condition, is a clean conversion method, can solve the environmental pollution and can generate high-efficiency new energy.
In recent years, zinc selenide as a II-VI semiconductor material has a wide development prospect and application potential in the fields of photoelectrocatalysis, photoelectric devices, photoluminescence and the like, and has attracted the research interest of scientists. However, the relatively wide forbidden band width of zinc selenide reduces the utilization rate of sunlight, and in order to reduce the band gap of zinc selenide and enhance the absorption of light, a continuously adjustable forbidden band width needs to be obtained through component adjustment, for example, a composite photocatalyst such as zinc cadmium sulfide, selenium cadmium sulfide and the like is obtained through component adjustment. However, the difficulty in preparing the composite photocatalyst is high, and the preparation method directly influences the catalytic activity, catalytic stability and other performances of the photocatalyst. Therefore, the development of the photocatalyst preparation method with low cost, mild and simple conditions has important significance in the aspects of controlling the micro-morphology of the composite photocatalyst material, adjusting the band gap and changing the visible light absorption, and can effectively improve the photocatalytic carbon dioxide reduction performance of the material.
Disclosure of Invention
The invention aims to provide a one-dimensional self-assembly photocatalyst, and a preparation method and application thereof, wherein the one-dimensional self-assembly photocatalyst is ZnxCd1-xSe photocatalyst and ZnxCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst has the advantages of simple reaction equipment, easiness in operation, low cost, mild reaction conditions, good dispersibility of the obtained photocatalyst product, high photocatalytic activity, good photocatalytic stability and good application prospect.
To achieve the purpose of the invention, the invention adopts one-dimensional self-assembly ZnxCd1-xThe preparation method of the Se photocatalyst comprises the following steps:
(1) fully dissolving a zinc source and sodium selenite in a water-organic amine-hydrazine hydrate ternary mixed solvent, uniformly stirring, transferring the solution into a drying oven, heating to 145-155 ℃, carrying out heat preservation reaction, cooling to room temperature after the reaction is finished, centrifugally washing a white precipitate, and drying by a freeze dryer to obtain a zinc selenide nanosheet;
(2) dissolving zinc selenide nanosheets in a water-organic amine binary mixed solvent, uniformly stirring, adding a cadmium source in a certain molar ratio, stirring for 1-3 hours, then transferring into an oven, heating to 145-155 ℃, carrying out heat preservation reaction for 6-10 hours, cooling to room temperature after the reaction is finished, and centrifugally washing dark redDrying the color precipitate by a freeze drier to obtain the selenium-cadmium-zinc nanostructure, namely the one-dimensional self-assembled ZnxCd1-xSe photocatalyst.
Furthermore, the invention also provides one-dimensional self-assembly ZnxCd1-xSe/Cu2Preparation method of O @ Cu composite photocatalyst, wherein Zn is self-assembled in one dimensionxCd1-xThe preparation method of the Se photocatalyst further comprises the following step (3): mixing Cu2Dispersing O @ Cu in secondary water, ultrasonically dispersing, adding the selenium cadmium zinc nanostructure obtained in the step (2), continuously ultrasonically stirring, washing, centrifuging, and drying in an oven to obtain one-dimensional self-assembled ZnxCd1-xSe/Cu2O @ Cu composite photocatalyst.
Further, in some embodiments of the invention, the Cu2The preparation method of O @ Cu comprises the following steps: a. dissolving anhydrous copper sulfate and polyethylene glycol in secondary water, stirring vigorously, adding ascorbic acid and sodium hydroxide after stirring and mixing uniformly; b. dissolving sodium borohydride in secondary water, slowly adding the solution obtained in the step a dropwise, stirring, centrifugally washing the dark green precipitate, and drying the dark green precipitate by a freeze dryer to obtain Cu2O@Cu。
Further, in some embodiments of the invention, x is 0 to 1.
Further, in some embodiments of the present invention, the selenium-cadmium-zinc nanostructures and the Cu in step (3)2The mass ratio of O @ Cu is 10: 1-4, preferably 10: 1.5-4.5, more preferably 10: 1.5-2.5.
Further, in some embodiments of the invention, the zinc source is zinc acetate or zinc chloride.
Further, in some embodiments of the present invention, the reaction time for the heat-preserving reaction in the step (1) is 10 to 14 hours, preferably 12 hours.
Further, in some embodiments of the present invention, the volume ratio of water, organic amine and hydrazine hydrate in the water-organic amine-hydrazine hydrate ternary mixed solvent is 16: 14: 5.
further, in some embodiments of the present invention, the cadmium source is cadmium acetate, cadmium chloride, or cadmium nitrate.
Further, in some embodiments of the present invention, the temperature in step (1) and step (2) is raised to 145-155 ℃ for the reaction, preferably 150 ℃.
Further, in some embodiments of the present invention, the reaction time for the heat-preserving reaction in the step (2) is 6 to 10 hours, preferably 8 hours.
Further, in some embodiments of the present invention, the organic amine in step (1) and step (2) is diethylenetriamine, triethylenetetramine and tetraethylenepentamine, preferably diethylenetriamine.
Further, in some embodiments of the present invention, the volume ratio of the water and the organic amine in the water-organic amine binary mixed solvent in the step (2) is 14: 6.
further, in some embodiments of the present invention, the molar ratio of zinc selenide to cadmium source in step (2) is 1: 0.3-0.7.
On the other hand, the invention also provides one-dimensional self-assembly ZnxCd1-xSe photocatalyst and one-dimensional self-assembled ZnxCd1-xSe/Cu2O @ Cu composite photocatalyst and one-dimensional self-assembly ZnxCd1-xSe photocatalyst and one-dimensional self-assembled ZnxCd1-xSe/Cu2The O @ Cu composite photocatalyst is prepared by the method.
In another aspect, the invention further provides the one-dimensional self-assembled ZnxCd1-xSe photocatalyst and one-dimensional self-assembled ZnxCd1-xSe/Cu2Application of O @ Cu composite photocatalyst, namely one-dimensional self-assembly ZnxCd1-xSe photocatalyst or one-dimensional self-assembled ZnxCd1-xSe/Cu2The O @ Cu composite photocatalyst is used in photocatalytic carbon dioxide reduction reaction.
Further, in some embodiments of the invention, the one-dimensional self-assembly of ZnxCd1-xSe photocatalyst and one-dimensional self-assembled ZnxCd1-xSe/Cu2O @ Cu composite photocatalyst for photocatalytic carbon dioxideThe method in the reduction reaction comprises the following steps: at room temperature, one-dimensional self-assembly ZnxCd1-xSe photocatalyst or ZnxCd1-xSe/Cu2Pouring the O @ Cu composite photocatalyst into a reactor, adding secondary water, carrying out ultrasonic treatment, drying the catalyst, placing the catalyst into a reactor for releasing carbon dioxide, and irradiating the reactor by using a xenon lamp with an optical filter.
Compared with the prior art, the invention has the following advantages:
(1) one-dimensional self-assembly Zn of the inventionxCd1-xSe photocatalyst or one-dimensional self-assembled ZnxCd1-xSe/Cu2The raw materials involved in the preparation method of the O @ Cu composite photocatalyst are non-noble metal salts, and the O @ Cu composite photocatalyst is low in price, rich in resources and wide in application.
(2) The hydrothermal reaction condition involved in the invention is mild, high temperature condition is not needed, and energy consumption is low.
(3) The catalyst prepared by the method has good dispersibility, high photocatalytic activity and good photocatalytic stability.
Drawings
FIG. 1 shows a one-dimensional self-assembled Zn obtained in example 5 of the present invention0.3Cd0.7Se/Cu2And (3) a transmission electron microscope photo of the O @ Cu composite photocatalyst.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention. It is to be understood that the following description is only illustrative of the present invention and is not to be construed as limiting the present invention.
The terms "comprises," "comprising," "includes," "including," "has," "having," "contains," "containing," or any other variation thereof, as used herein, are intended to cover a non-exclusive inclusion. For example, a composition, process, method, article, or apparatus that comprises a list of elements is not necessarily limited to only those elements but may include other elements not expressly listed or inherent to such composition, process, method, article, or apparatus.
Reference throughout this specification to "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" or the like means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above are not necessarily for the same embodiment or example. Further, the technical features of the embodiments of the present invention may be combined with each other as long as they do not conflict with each other.
If not specifically stated, the photocatalyst prepared by the invention is tested for catalytic performance by the following method: 50 mg of photocatalyst was poured into a reactor, followed by addition of 10 ml of secondary water and sonication for 30 minutes, the catalyst was removed, the catalyst was dried in an oven at 60 ℃, after which 0.12 g of sodium bicarbonate was added to the reactor, then the reactor was purged with nitrogen for 30 minutes and sealed, 0.5 ml of aqueous sulfuric acid (2M) was injected into the reactor and reacted with sodium bicarbonate to release carbon dioxide, and the reactor was illuminated with a 300 watt xenon lamp with a filter (wavelength greater than 420 nm).
Example 1
658.6 mg of zinc acetate and 518.8 mg of sodium selenite are placed in a water-organic amine-hydrazine hydrate ternary mixed solvent to be fully dissolved and uniformly stirred, the mixture is transferred into a drying oven, the temperature is raised to 150 ℃ and kept for 12 hours, the mixture is cooled to room temperature after the reaction is finished, white precipitate is centrifugally washed and dried by a freeze dryer, and the zinc selenide nanosheet is obtained.
Dissolving 43.3 mg of zinc selenide nanosheets in a water-organic amine binary mixed solvent, uniformly stirring, adding 20.6 mg of cadmium chloride, stirring for 3 hours, then transferring into an oven, heating to 150 ℃, keeping for 8 hours, cooling to room temperature after the reaction is finished, centrifugally washing dark red precipitates, and drying by a freeze dryer to obtain Zn0.7Cd0.3A Se nanostructure.
The one-dimensional self-assembled Zn prepared in the example0.7Cd0.3Se is applied to the photocatalytic carbon dioxide reduction reaction, the catalytic performance of Se is tested, and Zn is obtained through testing0.7Cd0.3The carbon monoxide yield of the Se nanostructure was 8.1. mu. mol/h/g.
Example 2
658.6 mg of zinc acetate and 518.8 mg of sodium selenite are placed in a water-organic amine-hydrazine hydrate ternary mixed solvent to be fully dissolved and uniformly stirred, the mixture is transferred into a drying oven, the temperature is raised to 150 ℃ and kept for 12 hours, the mixture is cooled to room temperature after the reaction is finished, white precipitate is centrifugally washed and dried by a freeze dryer, and the zinc selenide nanosheet is obtained.
Dissolving 43.3 mg of zinc selenide nanosheets in a water-organic amine binary mixed solvent, uniformly stirring, adding 34.2 mg of cadmium chloride, stirring for 3 hours, then transferring into an oven, heating to 150 ℃, keeping for 8 hours, cooling to room temperature after the reaction is finished, centrifugally washing dark red precipitates, and drying by a freeze dryer to obtain Zn0.5Cd0.5A Se nanostructure.
The carbon monoxide yield of the obtained selenium cadmium zinc nano structure is tested to be 9.3 mu mol/h/g.
Example 3
658.6 mg of zinc acetate and 518.8 mg of sodium selenite are placed in a water-organic amine-hydrazine hydrate ternary mixed solvent to be fully dissolved and uniformly stirred, the mixture is transferred into a drying oven, the temperature is raised to 150 ℃ and kept for 12 hours, the mixture is cooled to room temperature after the reaction is finished, white precipitate is centrifugally washed and dried by a freeze dryer, and the zinc selenide nanosheet is obtained.
Dissolving 43.3 mg of zinc selenide nanosheets in a water-organic amine binary mixed solvent, uniformly stirring, adding 47.9 mg of cadmium chloride, stirring for 3 hours, then transferring into an oven, heating to 150 ℃, keeping for 8 hours, cooling to room temperature after the reaction is finished, centrifugally washing dark red precipitates, and drying by a freeze dryer to obtain Zn0.3Cd0.7A Se nanostructure.
The carbon monoxide yield of the obtained selenium cadmium zinc nano structure is tested to be 13.3 mu mol/h/g.
Example 4
At room temperature, 798.1 mg of anhydrous copper sulfate and 6000 mg of polyethylene glycol are dissolved in 200 ml of secondary water and stirred vigorously, and after uniform mixing, 900 mg of ascorbic acid and 400 mg of sodium hydroxide are added to obtain a mixed solution.
Dissolving 400 mg of sodium borohydride in 50 ml of secondary water, slowly dripping the sodium borohydride into the mixed solution, stirring the mixture for 12 hours, centrifugally washing the dark green precipitate, and drying the dark green precipitate by a freeze dryer to obtain Cu2O@Cu。
Mixing 10 mg of Cu2Dispersing O @ Cu in 40 ml of secondary water, ultrasonically dispersing for 20 minutes, and adding 100 mg of one-dimensional self-assembly Zn0.3Cd0.7Se, continuing to perform ultrasonic treatment for 5 minutes, stirring for 30 minutes, washing, centrifuging, and drying in an oven at 60 ℃ to obtain the one-dimensional self-assembled ZnxCd1-xSe/Cu2O @ Cu composite photocatalyst.
Tested one-dimensional self-assembly ZnxCd1-xSe/Cu2The carbon monoxide yield of the O @ Cu composite photocatalyst is 36.4 mu mol/h/g.
Example 5
At room temperature, 798.1 mg of anhydrous copper sulfate and 6000 mg of polyethylene glycol are dissolved in 200 ml of secondary water and stirred vigorously, and after uniform mixing, 900 mg of ascorbic acid and 400 mg of sodium hydroxide are added to obtain a mixed solution.
Dissolving 400 mg of sodium borohydride in 50 ml of secondary water, slowly dripping the sodium borohydride into the mixed solution, stirring the mixture for 12 hours, centrifugally washing the dark green precipitate, and drying the dark green precipitate by a freeze dryer to obtain Cu2O@Cu。
20 mg of Cu2Dispersing O @ Cu in 40 ml of secondary water, ultrasonically dispersing for 20 minutes, and adding 100 mg of one-dimensional self-assembly Zn0.3Cd0.7Se, continuing to perform ultrasonic treatment for 5 minutes, stirring for 30 minutes, washing, centrifuging, and drying in an oven at 60 ℃ to obtain the one-dimensional self-assembled Zn0.3Cd0.7Se/Cu2O @ Cu composite photocatalyst.
Tested one-dimensional self-assembly Zn0.3Cd0.7Se/Cu2Carbon monoxide production of O @ Cu composite photocatalystThe ratio was 50.5. mu. mol/h/g.
Example 6
At room temperature, 798.1 mg of anhydrous copper sulfate and 6000 mg of polyethylene glycol are dissolved in 200 ml of secondary water and stirred vigorously, and after uniform mixing, 900 mg of ascorbic acid and 400 mg of sodium hydroxide are added to obtain a mixed solution.
Dissolving 400 mg of sodium borohydride in 50 ml of secondary water, slowly and dropwise adding the solution into the mixed solution, stirring for 12 hours, centrifugally washing the dark green precipitate, and drying the precipitate by a freeze dryer to obtain Cu2O@Cu。
Mixing 40 mg of Cu2Dispersing O @ Cu in 40 ml of secondary water, ultrasonically dispersing for 20 minutes, and adding 100 mg of one-dimensional self-assembly Zn0.3Cd0.7Se, continuing to perform ultrasonic treatment for 5 minutes, stirring for 30 minutes, washing, centrifuging, and drying in an oven at 60 ℃ to obtain the one-dimensional self-assembled Zn0.3Cd0.7Se/Cu2O @ Cu composite photocatalyst.
Tested one-dimensional self-assembly Zn0.3Cd0.7Se/Cu2The carbon monoxide yield of the O @ Cu composite photocatalyst is 46.0 mu mol/h/g.
It will be understood by those skilled in the art that the foregoing is only exemplary of the present invention, and is not intended to limit the invention, which is intended to cover any variations, equivalents, or improvements therein, which fall within the spirit and scope of the invention.
Claims (10)
1. One-dimensional self-assembly ZnxCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized by comprising the following steps:
(1) fully dissolving a zinc source and sodium selenite in a water-organic amine-hydrazine hydrate ternary mixed solvent, uniformly stirring, transferring the organic amine which is any one of diethylenetriamine, triethylene tetramine and tetraethylene pentamine into an oven, heating to 145-155 ℃, carrying out heat preservation reaction, cooling to room temperature after the reaction is finished, centrifugally washing a white precipitate, and drying by a freeze dryer to obtain a zinc selenide nanosheet;
(2) dissolving zinc selenide nanosheets in a water-organic amine binary mixed solvent, uniformly stirring, adding a cadmium source with a certain molar ratio into the zinc selenide nanosheets, stirring for 1-3 hours, transferring the zinc selenide nanosheets into an oven, heating to 145-155 ℃, carrying out heat preservation reaction for 6-10 hours, cooling to room temperature after the reaction is finished, centrifugally washing dark red precipitates, and drying by a freeze dryer to obtain a selenium-cadmium-zinc nanostructure, wherein the organic amine is any one of diethylenetriamine, triethylenetetramine and tetraethylenepentamine;
(3) mixing Cu2Dispersing O @ Cu in secondary water, ultrasonically dispersing, adding the selenium cadmium zinc nanostructure obtained in the step (2), continuously ultrasonically stirring, washing, centrifuging, and drying in an oven to obtain one-dimensional self-assembled ZnxCd1-xSe/Cu2O @ Cu composite photocatalyst.
2. One-dimensional self-assembled Zn according to claim 1xCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized in that the Cu is2The preparation method of O @ Cu comprises the following steps: a. dissolving anhydrous copper sulfate and polyethylene glycol in secondary water, stirring vigorously, adding ascorbic acid and sodium hydroxide after stirring and mixing uniformly; b. dissolving sodium borohydride in secondary water, slowly adding the solution obtained in the step a dropwise, stirring, centrifugally washing the dark green precipitate, and drying the dark green precipitate by a freeze dryer to obtain Cu2O@Cu。
3. One-dimensional self-assembled Zn according to claim 1xCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized in that x is 0-1; the selenium cadmium zinc nano structure and Cu in the step (3)2The mass ratio of O @ Cu is 10: 1-4.
4. One-dimensional self-assembled Zn according to claim 1xCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized in that the zinc source is zinc acetate or zinc chloride; the reaction time of the heat preservation reaction in the step (1) is 10-14 hours.
5. One-dimensional self-assembled Zn according to claim 1xCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized in that the volume ratio of water, organic amine and hydrazine hydrate in the water-organic amine-hydrazine hydrate ternary mixed solvent is 16: 14: 5; the cadmium source is cadmium acetate, cadmium chloride or cadmium nitrate; and (3) heating to 145-155 ℃ in the step (1) and the step (2) and carrying out heat preservation reaction.
6. One-dimensional self-assembled Zn according to claim 1xCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized in that the reaction time of the heat preservation reaction in the step (2) is 6-10 hours; the organic amine in the step (1) and the step (2) is diethylenetriamine.
7. One-dimensional self-assembled Zn according to claim 1xCd1-xSe/Cu2The preparation method of the O @ Cu composite photocatalyst is characterized in that the volume ratio of water to organic amine in the water-organic amine binary mixed solvent in the step (2) is 14: 6; the molar ratio of the zinc selenide to the cadmium source in the step (2) is 1: 0.3-0.7.
8. One-dimensional self-assembly ZnxCd1-xSe/Cu2The O @ Cu composite photocatalyst is characterized in that the one-dimensional self-assembly ZnxCd1-xSe/Cu2The O @ Cu composite photocatalyst is prepared by the method of any one of claims 1 to 7.
9. One-dimensional self-assembly ZnxCd1-xSe/Cu2The application of the O @ Cu composite photocatalyst is characterized in that the application comprises the following steps: the one-dimensional self-assembly Zn of claim 8xCd1-xSe/Cu2The O @ Cu composite photocatalyst is used in photocatalytic carbon dioxide reduction reaction.
10. One-dimensional self-assembly ZnxCd1-xSe/Cu2The method for applying the O @ Cu composite photocatalyst to photocatalytic carbon dioxide reduction reaction is characterized by comprising the following steps: at room temperature, one-dimensional self-assembly ZnxCd1-xSe/Cu2Pouring the O @ Cu composite photocatalyst into a reactor, adding secondary water, carrying out ultrasonic treatment, drying the catalyst, placing the catalyst into a reactor for releasing carbon dioxide, and irradiating the reactor by using a xenon lamp with an optical filter, wherein the one-dimensional self-assembly ZnxCd1-xSe/Cu2The O @ Cu composite photocatalyst is one-dimensional self-assembled Zn defined in claim 8xCd1-xSe/Cu2O @ Cu composite photocatalyst.
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