CN116237063B - Yttrium promoted carbon dioxide reduction catalyst and its preparation method - Google Patents
Yttrium promoted carbon dioxide reduction catalyst and its preparation method Download PDFInfo
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- CN116237063B CN116237063B CN202310134125.2A CN202310134125A CN116237063B CN 116237063 B CN116237063 B CN 116237063B CN 202310134125 A CN202310134125 A CN 202310134125A CN 116237063 B CN116237063 B CN 116237063B
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 71
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 57
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 230000009467 reduction Effects 0.000 title claims abstract description 53
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 13
- 238000006722 reduction reaction Methods 0.000 claims description 57
- 239000010949 copper Substances 0.000 claims description 39
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 239000002243 precursor Substances 0.000 claims description 35
- 239000000758 substrate Substances 0.000 claims description 32
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- 229910052717 sulfur Inorganic materials 0.000 claims description 19
- 239000011593 sulfur Substances 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- 239000004744 fabric Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000006260 foam Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical group [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 7
- 239000002135 nanosheet Substances 0.000 claims description 7
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical group S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 238000003717 electrochemical co-deposition Methods 0.000 claims description 3
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000002064 nanoplatelet Substances 0.000 abstract 1
- 229910000510 noble metal Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 18
- 239000000047 product Substances 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 229910052761 rare earth metal Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 238000001035 drying Methods 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 238000013507 mapping Methods 0.000 description 7
- 150000002910 rare earth metals Chemical class 0.000 description 6
- 238000004073 vulcanization Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 229910052697 platinum Inorganic materials 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910017604 nitric acid Inorganic materials 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000007740 vapor deposition Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 230000002401 inhibitory effect Effects 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007806 chemical reaction intermediate Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/33—
Abstract
The invention discloses a carbon dioxide reduction catalyst and a preparation method and application thereof. The carbon dioxide reduction catalyst comprises yttrium and copper sulfide. Yttrium-substituted doped copper sulfide of a nano-platelet structure is formed. The carbon dioxide reduction catalyst is a non-noble metal high-activity carbon dioxide reduction catalyst, has good multi-carbon product ethanol selectivity and large surface area, and simultaneously has a large number of active sites, so that the carbon dioxide reduction catalyst has good reduction catalytic performance and can inhibit competing hydrogen evolution reaction.
Description
Technical Field
The invention belongs to the field of electrochemical catalysis, and particularly relates to a carbon dioxide reduction catalyst, a preparation method thereof and application thereof in carbon dioxide reduction.
Background
With the growing world population and the decreasing natural vegetation, carbon recycling economy has become one of the biggest challenges facing humans, renewable electrical energy driving electrochemical carbon dioxide reduction (CO 2 RR), provides an effective way to reduce global carbon dioxide. Copper exhibits unique physical, chemical and electronic properties due to its four chemical states of zero, monovalent, divalent and trivalent (minor amounts). Therefore, copper is widely dispersed on a carrier in chemical reaction to prepare a copper-based catalyst, and the copper-based catalyst is applied to hydrogenation, dehydrogenation, coupling, photoelectrocatalysis and other reactions. Electrocatalytic carbon dioxide reduction reactions can convert CO 2 Conversion to valuable chemicals, which are currently capable of reducing CO 2 One of the emissionsA gentle and sustainable way. Since the carbon dioxide reduction reaction has many reaction paths and reaction intermediates are complicated, the variety of products is large and the control of the selectivity of a specific product is a great challenge.
Disclosure of Invention
Based on the above-mentioned problems in the prior art, it is an object of the present invention to provide a carbon dioxide reduction catalyst, a method for preparing the carbon dioxide reduction catalyst, a method for reducing carbon dioxide, and a fourth object of the present invention is to provide an application of the carbon dioxide reduction catalyst in reducing carbon dioxide.
In a first aspect, the present invention provides a carbon dioxide reduction catalyst comprising yttrium and copper sulphide. According to the invention, through doping of rare earth yttrium, the energy band of copper sulfide is regulated and controlled by utilizing a special 4f-5d structure of rare earth metal, the selectivity of a reduction product of copper sulfide can be obviously improved, and the catalytic stability of the reduction product is facilitated to be improved, so that the carbon dioxide reduction catalyst has excellent electrocatalytic reduction product selectivity and hydrogen evolution competition reaction inhibiting capability.
According to some embodiments of the invention, the yttrium and copper sulfide form yttrium doped copper sulfide. According to some embodiments of the invention, the yttrium and copper sulfide form yttrium-substituted doped copper sulfide.
According to some embodiments of the invention, the yttrium and copper sulfide are yttrium doped copper sulfide nano-sheets, and the nano-sheet structure can effectively improve the specific surface area of the catalyst and further improve the reduction reaction activity.
According to some embodiments of the invention, the molar content of yttrium is 5% -30%, for example 5%, 10%, 15%, 20%, 30% or any value in between, based on the total amount of yttrium and copper sulphide. In some preferred embodiments, the molar content of yttrium is 5% to 20%, more preferably 5% to 15%, still more preferably 8% to 12%, based on the total amount of yttrium and copper sulfide. The inventors have found that in the carbon dioxide reduction catalyst, the molar content of yttrium affects the reduction performance of the catalyst, and that a catalyst having the molar content of yttrium controlled within the above range, particularly controlled within the range of 8-12%, has more excellent performance in reducing carbon dioxide.
In some embodiments, the molar content of yttrium is about 5% based on the total amount of yttrium and copper sulfide. In some embodiments, the molar content of yttrium is about 15% based on the total amount of yttrium and copper sulfide. In some embodiments, the molar content of yttrium is about 10% based on the total amount of yttrium and copper sulfide.
According to some embodiments of the invention, the catalyst further comprises a substrate, the yttrium and copper sulfide being supported on the substrate. In some embodiments, the substrate is a conductive substrate FTO. In some embodiments, the substrate is selected from one or more of carbon cloth, foam nickel.
According to some embodiments of the invention, the copper sulfide is supported on the substrate at a loading of 2mg/cm 2 -10mg/cm 2 For example 2.5mg/cm 2 、3.0mg/cm 2 、3.5mg/cm 2 、4.0mg/cm 2 、4.5mg/cm 2 、5.0mg/cm 2 、6.0mg/cm 2 、7.0mg/cm 2 、8.0mg/cm 2 、9.0mg/cm 2 、9.5mg/cm 2 Or any value therebetween. In some embodiments of the invention, the copper sulfide is present on the substrate at a loading of 2mg/cm 2 -8.5mg/cm 2 . In some embodiments, the copper sulfide is present on the substrate at a loading of 2.5mg/cm 2 -5.0mg/cm 2 。
In a second aspect, the present invention provides a method of preparing a carbon dioxide reduction catalyst comprising sulfiding a precursor comprising a source of yttrium and a source of copper.
In some embodiments, the precursor is sulfided, the precursor being yttrium doped copper.
In some embodiments, the sulfiding comprises maintaining the precursor at 200 ℃ to 500 ℃ for 1h to 8h, preferably at 250 ℃ to 350 ℃ for 1h to 5h, in the presence of a sulfur source. According to some embodiments of the invention, the sulfiding comprises heating the precursor to 300 ℃ in an inert atmosphere in the presence of a sulfur source, for 2 hours.
According to some embodiments of the invention, the vulcanization is performed in an inert atmosphere.
According to some embodiments of the invention, the vulcanization is achieved using a tube furnace.
According to some embodiments of the invention, the preparation of the precursor comprises: the substrate is placed in sequence in a solution containing a copper source and an yttrium source for electrochemical co-deposition. In some embodiments, electrochemical codeposition is performed by a three electrode system. Ag/AgCl is used as a reference electrode, platinum is used as a counter electrode, and a substrate is used as a working electrode.
According to some embodiments of the invention, the preparation of the precursor comprises the steps of:
the precursor is obtained by placing the substrate in a solution containing a copper source and an yttrium source and depositing 1000s-7000s (e.g. 1000s, 3000s, 5000s, 7000s or any value in between) at a potential of-0.6V to-1.5V (e.g. of-0.7V, -0.9V, -1.1V, -1.3V, -1.5V or any value in between). In some embodiments, the precursor comprises a substrate deposited with cuprous hydroxide and/or elemental copper.
According to some embodiments of the invention, the preparation of the precursor comprises the steps of:
the precursor is obtained by placing the substrate in a solution containing a copper source and an yttrium source and depositing at a potential of-0.9V to-1.2V for 2000s-5000s, preferably at a potential of-1.0V to-1.1V for 3000s-4000 s.
According to some embodiments of the invention, the method of preparing the above-described catalyst comprises first depositing a copper source and an yttrium source simultaneously on a substrate using electrochemical co-deposition, and then effecting sulfidation. In the invention, electrochemical codeposition is carried out on a copper source and an yttrium source, thereby realizing an atom-substituted rare earth doping form on the copper source, and the doping form plays a decisive role in the reduction process.
According to some embodiments of the invention, the molar content of yttrium is 5% -30%, for example 5%, 10%, 15%, 20%, 30% or any value in between, based on the total amount of yttrium element and copper element. According to some preferred embodiments of the present invention, the molar content of yttrium is 5% to 20%, more preferably 5% to 15%, still more preferably 8% to 12% based on the total amount of yttrium element and copper element.
According to some embodiments of the invention, the sulfur source is in excess compared to the mass of the copper source. According to some embodiments of the invention, the molar ratio of the sulfur source to the copper source is (1000-5000): 1, for example 1000:1, 2000:1, 3000:1, 4000:1, 5000:1 or any value therebetween. According to some embodiments of the invention, the molar ratio of the sulfur source to the copper source is (1000-3000): 1.
according to some embodiments of the invention, the sulfur source is 100-1000mg, e.g., 100mg, 200mg, 400mg, 500mg, 700mg, 900mg, 1000mg, etc. According to some preferred embodiments of the invention, the sulphur source is 200-800mg, more preferably 300-500mg, wherein the sulphur source is in excess.
According to some embodiments of the invention, the yttrium source is selected from yttrium nitrate and/or yttrium chloride, preferably from yttrium nitrate.
According to some embodiments of the invention, the copper source is selected from copper nitrate and/or copper chloride, preferably from copper nitrate.
According to some embodiments of the invention, the sulfur source is selected from sulfur powder.
According to some embodiments of the invention, the substrate is selected from one or more of carbon cloth, nickel foam, and conductive glass. In some embodiments, the substrate is nickel foam. In some embodiments, the substrate is a carbon cloth. In some embodiments, the substrate is a conductive glass.
According to some embodiments of the invention, the method for preparing the carbon dioxide reduction catalyst comprises the following specific steps:
step S1: placing the substrate in acid liquor for ultrasonic treatment, washing with an organic solvent and water and drying;
step S2: placing the substrate dried in the step S1 into a solution containing a copper source and an yttrium source, and performing electrochemical codeposition through a three-electrode system to obtain a precursor;
step S3: washing and drying the precursor obtained in the step S2, preferably putting the precursor into a vacuum oven and drying the precursor for 1 to 4 hours at 30 to 80 ℃, more preferably drying the precursor for 2 to 3 hours at 50 to 60 ℃;
step S4: and (3) placing the precursor treated in the step (S3) in a tube furnace, adding sublimed sulfur, and reacting with high-temperature inert gas to obtain the carbon dioxide reduction catalyst.
The carbon dioxide reduction catalyst is prepared by an electrochemical codeposition method, and is simple and quick to operate.
In a third aspect, the present invention provides a method of reducing carbon dioxide, the method comprising subjecting carbon dioxide to a reduction reaction in the presence of a carbon dioxide reduction catalyst as described above.
In some embodiments, the reduction reaction is a carbon dioxide electrochemical reduction reaction.
In a fourth aspect, the present invention provides the use of a carbon dioxide reduction catalyst as described above or as prepared by a method as described above as an electrocatalytic carbon dioxide reduction catalyst, or the use of a method as described in the third aspect in carbon dioxide reduction.
The carbon dioxide reduction catalyst provided by the invention comprises a substrate and yttrium doped copper sulfide grown on the substrate. The reduction catalyst is a carbon dioxide reduction catalyst with high activity of rare earth metal, has good oxidation resistance and large surface area, and simultaneously has a large number of active sites, so that the catalyst has good reduction catalytic performance. In addition, the carbon dioxide reduction catalyst has good stability.
Drawings
FIG. 1 is an X-ray diffraction pattern of the product prepared in example 1.
FIG. 2 is a transmission electron micrograph of the product prepared in example 1.
Fig. 3 is an EDS spectrum of the product obtained in example 1, wherein a shows the superimposed distribution of copper, sulfur and yttrium, B shows the distribution of copper, C shows the distribution of sulfur, and D shows the superimposed distribution of yttrium.
Fig. 4 is an atomic phase Mapping diagram of the product prepared in example 1, in which a shows atomic phase Mapping of copper element, B shows atomic phase Mapping of yttrium element, C shows atomic phase Mapping of sulfur element, D shows superimposed atomic phase Mapping of sulfur element and copper element, and E shows superimposed atomic phase Mapping of copper element, sulfur element and yttrium element.
FIG. 5 is an in-situ fluorescence spectrum of the product prepared in example 1.
Fig. 6 is a linear sweep voltammetry curve of the products prepared in examples 1 to 3 and comparative example 1 as a catalyst to promote the reduction reaction.
FIG. 7 is a bar graph showing the ethanol selectivity of the products of the catalytic carbon dioxide reduction reaction of the products prepared in example 1 and comparative example 1.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. The specific embodiments described herein are for purposes of illustration only and are not to be construed as limiting the invention in any way. In addition, in the following description, descriptions of well-known structures and techniques are omitted so as not to unnecessarily obscure the concepts of the present disclosure. Such structures and techniques are also described in a number of publications.
The present invention will be further illustrated by the following specific examples, but the scope of the present invention is not limited thereto.
Ultrapure water with the conductivity of 18.25MΩ is used in the experimental process, and all reagents used in the experiment are analytically pure.
The main instruments and reagents used:
the CHI760E electrochemical workstation (Shanghai Chen Hua instruments Co.) is used for linear sweep voltammetry test;
the ultra-pure water device of Utility laboratory (Chengdu ultra-pure technology Co., ltd.) is used for preparing ultra-pure water;
an electronic balance (Shanghai platinum mechanical equipments Co., ltd.) for weighing the medicine;
table X-ray diffractometer (MiCuFlex 600, co., ltd.) for X-ray diffraction characterization;
the transmission electron microscope is used for representing the morphology of the reduction catalyst;
a steady state/transient fluorescence/phosphorescence spectrometer (HORIBA INSTRUMENTS INCORPORATED) for in situ fluorescence characterization;
vacuum drying oven (Shanghai-constant scientific instruments Co., ltd.);
KQ5200 ultrasonic cleaner (Kunshan ultrasonic instruments Co., ltd.);
working electrode: a three-electrode system, ag/AgCl (CHI instruments Co., USA) as a reference electrode and platinum as a counter electrode;
bench type drying oven (Chongqing test equipment factory);
copper nitrate (Chengdu Kelong chemical institute);
yttrium nitrate (beijing enoki technology limited);
carbon cloth (Shanghai Hesen electric Co., ltd.), conductive glass (Zhuhai Kai electronic components Co., ltd., model FTO-P002), foam nickel (Guangshengjia New Material Co., ltd.).
The yttrium and copper sulfide content was obtained by inductively coupled plasma (ICP-OES) testing.
Example 1
A piece of carbon cloth of 2cm by 3cm was put into a 1M nitric acid solution for ultrasonic treatment for several minutes, taken out, washed with ethanol and water for several times, and dried in a vacuum drying oven at 50 ℃.
50mL of 0.1M Cu (NO) 3 ) 2 ·6H 2 O aqueous solution, 5mL of 0.1M Y (NO) 3 ) 3 ·5H 2 Placing the O aqueous solution in a 100mL beaker, immersing the pretreated carbon cloth material in the solution, connecting with a working electrode, taking out after reacting for 3600s under the voltage of-1.0V, cleaning with deionized water, and then drying in a vacuum oven at 50 ℃ for 2h to obtain the nano sheet-shaped precursor.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 300mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth element yttrium doped copper sulfide with the nano-sheet structure, namely Y-CuS.
In the Y-CuS, the molar content of Y is 9.8 percent based on the total amount of yttrium and copper sulfide, and the loading amount of copper sulfide on the carbon cloth is 3.5mg/cm 2 。
The X-ray diffraction pattern of the final product obtained in this example is shown in FIG. 1, in which the card JCPDS303-1090 is assigned to the diffraction peak of CuS. The Y-CuS electron microscope photograph is shown in FIG. 2, and the EDS energy spectrum is shown in FIG. 3, which shows that rare earth Y is uniformly doped into copper sulfide. Wherein the atomic phase Mapping of Y-CuS is shown in FIG. 4, which shows that rare earth Y is doped into the crystal lattice in the form of atom substitution. As shown in FIG. 5, the in-situ fluorescence spectrum is changed, so that the deposition of yttrium is beneficial to regulating and controlling the energy level structure of copper sulfide and inhibiting competing hydrogen evolution reaction, so that the electrocatalytic activity and selectivity of the copper sulfide are improved.
Example 2
A piece of 2cm by 3cm of foamed nickel was put into a 1M nitric acid solution for ultrasonic treatment for several minutes, taken out, washed with ethanol and water for several times, and dried in a vacuum drying oven at 50 ℃.
50mL of 0.1M Cu (NO) 3 ) 2 ·6H 2 O aqueous solution, 2.5mL of 0.1M Y (NO) 3 ) 3 ·5H 2 Placing the O aqueous solution in a 100mL beaker, immersing the pretreated foam nickel material in the solution, connecting with a working electrode, taking out after reacting for 3600s under the voltage of-0.8V, cleaning with deionized water, and then drying in a vacuum oven at 50 ℃ for 2h to obtain the nano sheet-shaped precursor.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 500mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth element yttrium doped copper sulfide with the nano-sheet structure, namely Y-CuS.
In Y-CuS, the molar content of Y is 5.3 percent based on the total amount of yttrium and copper sulfide, and the loading of copper sulfide on foam nickel is 2.6mg/cm 2 。
Example 3
A piece of conductive glass of 2cm by 2cm was put into a 1M nitric acid solution for ultrasonic treatment for several minutes, taken out, washed with ethanol and water for several times, and dried in a vacuum drying oven at 50 ℃.
50mL of 0.1M Cu (NO) 3 ) 2 ·6H 2 O aqueous solution, 7.5mL of 0.1M Y (NO) 3 ) 3 ·5H 2 The O aqueous solution is placed in a 100mL beaker, the pretreated conductive glass is immersed in the solution and connected with a working electrode, the reaction is carried out for 3600s under the voltage of 1.2V, the solution is taken out and washed by deionized water, and then the solution is dried in a vacuum oven at 50 ℃ for 2h, so that the nano flaky precursor is obtained.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 100mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the rare earth element yttrium doped copper sulfide with the nano-sheet structure, namely Y-CuS.
In the Y-CuS, the molar content of Y is 14.8 percent based on the total amount of yttrium and copper sulfide, and the loading amount of copper sulfide on the conductive glass is 4.2mg/cm 2 。
Comparative example 1
A piece of carbon cloth of 2cm by 3cm was put into a 1M nitric acid solution for ultrasonic treatment for several minutes, taken out, washed with ethanol and water for several times, and dried in a vacuum drying oven at 50 ℃.
50mL of 0.1M Cu (NO) 3 ) 2 ·6H 2 Placing O aqueous solution in a 100mL beaker, immersing the pretreated carbon cloth material in the solution, connecting with a working electrode, taking out after reacting for 3600s under the voltage of-1.0V, washing with deionized water, and then drying in a vacuum oven at 50 ℃ for 2h to obtain the nano sheet-shaped precursor.
The vulcanization process is carried out in a vacuum tube furnace of a vapor deposition system. The precursor and 300mg of sulfur powder are added into a vacuum tube furnace, and argon is introduced to an atmospheric pressure steady state after the tube furnace is vacuumized. Heating to 300 ℃ at a heating rate of 10 ℃/min, reacting for 2 hours, and cooling to room temperature at a cooling rate of 100 ℃/h to obtain the copper sulfide with the nano-sheet structure, namely CuS.
Test example 1
The products obtained in example 1, example 2, example 3 and comparative example 1 were each sheared into a three-electrode system of 0.5cm×1cm sandwiched between electrode clamps as a working electrode, platinum as a counter electrode and Ag/AgCl as a reference electrode, and the three-electrode system was inserted into a potassium bicarbonate solution of 0.5M in mass concentration to conduct carbon dioxide reduction reaction under a proton exchange membrane, wherein the working electrode and the reference electrode were on one side of the membrane and the counter electrode was on the other side. Scanning in the range of potential window-0.8V to-1.8V at a scanning speed of 2mV/s gives a linear sweep voltammetry curve for the reduction reaction, as shown in FIG. 6.
Test example 2
The products obtained in example 1 and comparative example 1 were sheared into a three-electrode system of 0.5cm x 1cm sandwiched between electrode clamps as working electrode, platinum as counter electrode and Ag/AgCl as reference electrode, and the three-electrode system was inserted into a potassium bicarbonate solution having a mass concentration of 0.5M for the selectivity test, wherein the working electrode and the reference electrode were on one side of the proton exchange membrane and the counter electrode was on the other side. The reaction was carried out for 3 hours in the range of-0.8V to-1.8V, respectively, to obtain a Faraday efficiency selectivity test histogram of the product solution for determining ethanol by nuclear magnetism, as shown in FIG. 7.
As can be seen from the above test examples and FIGS. 6 to 7, the carbon dioxide reduction catalyst of the present invention has excellent electrocatalytic activity. The carbon dioxide reduction catalyst of the invention has large surface area and a large number of active sites, and the factors lead the catalyst to have good carbon dioxide reduction catalytic performance. In addition, the carbon dioxide reduction catalyst provided by the invention has good selectivity and capability of inhibiting competing hydrogen evolution reaction.
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (18)
1. A carbon dioxide reduction catalyst comprises a substrate, yttrium and copper sulfide, wherein the yttrium and the copper sulfide are loaded on the substrate, the yttrium and the copper sulfide form yttrium-substituted doped copper sulfide, the yttrium and the copper sulfide form a nano-sheet structure, and the molar content of the yttrium is 5% -30% based on the total amount of the yttrium and the copper sulfide.
2. The carbon dioxide reduction catalyst according to claim 1, wherein the molar content of yttrium is 5% -20% based on the total amount of yttrium and copper sulfide.
3. The carbon dioxide reduction catalyst according to claim 1, characterized in that the molar content of yttrium is 8% -15% based on the total amount of yttrium and copper sulphide.
4. A carbon dioxide reduction catalyst according to any one of claims 1 to 3, wherein the substrate is selected from one or more of carbon cloth, nickel foam and conductive glass.
5. The carbon dioxide reduction catalyst according to claim 4, wherein the copper sulfide is supported on the substrate at a loading of 2mg/cm 2 -10 mg/cm 2 。
6. The carbon dioxide reduction catalyst according to claim 4A catalyst, characterized in that the loading of the copper sulfide on the substrate is 2.5mg/cm 2 -5 mg/cm 2 。
7. A method of preparing the carbon dioxide reduction catalyst of any one of claims 1-6, comprising sulfiding a precursor comprising a yttrium source and a copper source, the preparing of the precursor comprising: the substrate is placed in a solution containing a yttrium source and a copper source and subjected to electrochemical co-deposition.
8. The method of claim 7, wherein the sulfiding comprises maintaining the precursor at 200 ℃ to 500 ℃ for 1h to 8h in the presence of a sulfur source.
9. The method of claim 8, wherein the sulfiding comprises maintaining the precursor at 250 ℃ to 350 ℃ for 1h to 5h in the presence of a sulfur source.
10. The method of preparing according to claim 7, wherein the preparation of the precursor comprises the steps of:
the substrate is placed in a solution containing a yttrium source and a copper source and deposited at a potential of-0.6V to-1.5V for 1000s-7000s to obtain the precursor.
11. The method of preparing according to claim 7, wherein the preparation of the precursor comprises the steps of:
the substrate is placed in a solution containing a yttrium source and a copper source and deposited at a potential of-0.9V to-1.2V for 2000s-5000s to obtain the precursor.
12. The method of preparing according to claim 7, wherein the preparation of the precursor comprises the steps of:
the substrate is placed in a solution containing a yttrium source and a copper source and deposited at a potential of-1.0V to-1.1V for 3000s-4000s to obtain the precursor.
13. The method according to any one of claims 7 to 12, wherein the molar content of the yttrium source is 5% to 30% based on the total amount of yttrium element and copper element;
and/or the sulfur source is in excess compared to the mass of the copper source;
and/or the sulfur source has a mass of 100-1000mg.
14. The method of claim 13, wherein the yttrium source is present in an amount of 5% to 20% by mole based on the total amount of yttrium and copper;
and/or the sulfur source has a mass of 200-800mg.
15. The method according to claim 13, wherein the yttrium source is present in an amount of 8% to 15% by mole based on the total amount of yttrium and copper;
and/or the sulfur source has a mass of 300-500mg.
16. The method of any one of claims 7-12, wherein the yttrium source is selected from yttrium nitrate and/or yttrium chloride;
and/or the copper source is selected from copper nitrate and/or copper chloride;
and/or the sulfur source is selected from sulfur powder;
and/or the substrate is selected from one or more of carbon cloth, foam nickel and conductive glass.
17. A method for carbon dioxide reduction, comprising subjecting carbon dioxide to a reduction reaction in the presence of the carbon dioxide reduction catalyst according to any one of claims 1 to 6 or the carbon dioxide reduction catalyst prepared according to the preparation method of any one of claims 7 to 16.
18. Use of the carbon dioxide reduction catalyst of any one of claims 1 to 6 or the carbon dioxide reduction catalyst prepared by the method of any one of claims 7 to 16 as an electrocatalytic carbon dioxide reduction catalyst or the method of claim 17 in carbon dioxide reduction.
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