CN109675586A - The catalyst and preparation method thereof of electroreduction carbon dioxide formic acid - Google Patents
The catalyst and preparation method thereof of electroreduction carbon dioxide formic acid Download PDFInfo
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- CN109675586A CN109675586A CN201811597998.2A CN201811597998A CN109675586A CN 109675586 A CN109675586 A CN 109675586A CN 201811597998 A CN201811597998 A CN 201811597998A CN 109675586 A CN109675586 A CN 109675586A
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- Prior art keywords
- catalyst
- formic acid
- carbon dioxide
- electroreduction
- chalcogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 55
- RWYPDBKDTQPOSR-UHFFFAOYSA-N OC=O.O=C=O Chemical compound OC=O.O=C=O RWYPDBKDTQPOSR-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 56
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052798 chalcogen Inorganic materials 0.000 claims abstract description 28
- 150000001787 chalcogens Chemical class 0.000 claims abstract description 28
- 235000019253 formic acid Nutrition 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 27
- 239000002184 metal Substances 0.000 claims abstract description 27
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 16
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 150000003839 salts Chemical class 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000005864 Sulphur Substances 0.000 claims abstract description 6
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000011669 selenium Substances 0.000 claims abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 5
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 5
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 4
- 229910052714 tellurium Inorganic materials 0.000 claims abstract description 4
- 239000012702 metal oxide precursor Substances 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 51
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 49
- 229910052799 carbon Inorganic materials 0.000 claims description 41
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 25
- 239000001569 carbon dioxide Substances 0.000 claims description 24
- 239000003792 electrolyte Substances 0.000 claims description 24
- 239000011736 potassium bicarbonate Substances 0.000 claims description 19
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 19
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000010439 graphite Substances 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 8
- 239000004744 fabric Substances 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229910000025 caesium bicarbonate Inorganic materials 0.000 claims description 3
- 229940091258 selenium supplement Drugs 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 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
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 229960001471 sodium selenite Drugs 0.000 claims description 2
- 235000015921 sodium selenite Nutrition 0.000 claims description 2
- 239000011781 sodium selenite Substances 0.000 claims description 2
- SITVSCPRJNYAGV-UHFFFAOYSA-N tellurous acid Chemical compound O[Te](O)=O SITVSCPRJNYAGV-UHFFFAOYSA-N 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000009257 reactivity Effects 0.000 abstract description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 230000004044 response Effects 0.000 description 10
- 238000001228 spectrum Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 10
- 239000010935 stainless steel Substances 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- PSCMQHVBLHHWTO-UHFFFAOYSA-K Indium trichloride Inorganic materials Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 description 7
- 238000004445 quantitative analysis Methods 0.000 description 7
- 238000007789 sealing Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- 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
- B01J27/0576—Tellurium; 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
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The catalyst and preparation method thereof of electroreduction carbon dioxide formic acid, belong to electro-catalysis field, the catalyst is the metal elctro-catalyst of chalcogen doping, and chalcogen includes at least one of sulphur, selenium and tellurium, and metal includes at least one of indium, tin, lead and bismuth；1) preparation method with dissolving metal salts in n,N-Dimethylformamide by the compound of the simple substance of chalcogen or chalcogen the following steps are included: will be then placed in carbon material, and be transferred in autoclave and carry out solvent heat treatment；2) carbon material is taken out after solvent heat treatment, and is washed with deionized, dry to get the metal oxide precursor adulterated to carbon material supported chalcogen, the metal elctro-catalyst that then electroreduction adulterates up to carbon material supported chalcogen.The catalyst is applied in the reaction of electroreduction carbon dioxide formic acid, and reactivity is high, and selectivity is high, stable in catalytic performance, and very high formic acid selectivity is maintained in very wide current range.
Description
Technical field
The invention belongs to the catalyst and its preparation side of electro-catalysis field more particularly to electroreduction carbon dioxide formic acid
Method.
Background technique
It by catalysis transform of carbon dioxide at the chemicals or fuel of high added value, can both turn waste into wealth, and reduce titanium dioxide
Carbon emission, and renewable energy can be changed into the fuel storage of high-energy density, it has important practical significance.Electric energy can be with
It is generated from renewable energy such as solar energy and wind energy, has many advantages, such as to clean, is mild, sustainable.Therefore, pass through electrochemical method
It is important fuel or chemicals by carbon dioxide conversion, is the most attractive approach realizing Resources of Carbon Dioxide and utilizing
One of.
By the energy for comparing electroreduction carbon dioxide difference product (such as carbon monoxide, methane, formic acid, ethane and ethylene)
Amount input cost and the market price, formic acid are a kind of products the most economically viable.Moreover, formic acid is as a kind of important industry
Raw material has important role in terms of pharmacy, leather and papermaking, further, it is also possible to fire as hydrogen carrier for direct formic acid
Expect battery.
The significant challenge of electroreduction carbon dioxide formic acid develops high activity, highly selective and high stability at present
Elctro-catalyst.Although certain catalyst are available higher by the modulation to catalyst structure, pattern and composition etc.
Carbon dioxide reduction selectivity, but it is highly selective very sensitive to the electric current and current potential of application.Due under high current density (>
60mA cm-2) the active raising of competitive reaction evolving hydrogen reaction, formic acid faradic efficiency significantly reduces, so that the generation of formic acid
Rate is difficult to break through 1000 μm of ol h-1cm-2。
Therefore, electroreduction carbon dioxide formic acid activity can be obviously improved while keep high formic acid selectivity by developing one kind
Seem particularly significant with the catalyst of stability.
Summary of the invention
It is an object of the invention to solve the above problem in the prior art, urging for electroreduction carbon dioxide formic acid is provided
Agent and preparation method thereof, catalyst reaction activity is high, and selectivity is high, stable in catalytic performance, and in very wide current range
Maintain very high formic acid selectivity.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
The catalyst of electroreduction carbon dioxide formic acid is the metal elctro-catalyst of chalcogen doping in the present invention, described
Chalcogen includes at least one of sulphur, selenium and tellurium, and the metal includes at least one of indium, tin, lead and bismuth；Sulfur family member
The content molar percentage of element is 0.01%~25%.
The preparation method of the catalyst of electroreduction carbon dioxide formic acid, comprising the following steps:
1) first by the compound and dissolving metal salts of the simple substance of chalcogen or chalcogen in N, N- dimethyl methyl
In amide, it is then placed in carbon material, is finally transferred in the stainless steel autoclave of polytetrafluoro liner and carries out solvent heat treatment；
2) after solvent heat treatment, carbon material is first taken out, and be washed with deionized, it is dry to get negative to carbon material
The metal oxide precursor of the chalcogen doping of load, the gold that then electroreduction adulterates up to carbon material supported chalcogen
Belong to elctro-catalyst.
The carbon material includes at least one of carbon paper, carbon cloth, graphite flake, foamy carbon, carbon nanotube.More preferably, institute
Carbon material is stated using carbon paper.
The compound of the chalcogen is selected from sulphur powder, thiocarbamide, vulcanized sodium, thioacetamide, selenium powder, sodium selenite, tellurium
At least one of powder, tellurous acid.
The metal salt is selected from least one of indium, tin, lead and chlorate, nitrate and the acetylacetonate of bismuth.
The temperature of solvent heat treatment is 130~200 DEG C, and the time of solvent heat treatment is 12~48h, and electroreduction handles current potential
For -0.98V vs.RHE.
The content of chalcogen can be by changing chalcogen in the metal elctro-catalyst of the chalcogen doping
The feed ratio of the compound and metal salt of simple substance or chalcogen is realized.
The catalyst of electroreduction carbon dioxide formic acid is applied in electroreduction carbon dioxide formic acid, in H-type electrolytic cell
In reacted, the metal elctro-catalyst of chalcogen doping does cathode, and Pt piece or graphite do anode, saturated calomel electrode
Reference electrode is done, carbon dioxide is passed through in catholyte with certain flow velocity, applies negative potential and is electrolysed, obtain first
Acid.
Carbon dioxide flow rate is 5~100mL min-1；Electrolyte includes NaHCO3、KHCO3、CsHCO3And K2SO4In extremely
Few one kind, concentration of electrolyte are 0.1~2M；Negative potential is -0.33~-1.23V vs.RHE.
Electrochemical reaction in the present invention includes:
Cathode reaction CO2+H2O+2e-→HCOO-+OH-；
Anode reaction 4OH-→O2+2H2O+4e-；
Overall reaction 2CO2+2OH-→2HCOO-+O2。
Compared with the existing technology, the beneficial effect that technical solution of the present invention obtains is:
Method for preparing catalyst of the invention is simple and easy；Compared with existing electroreduction formic acid system, present invention catalysis
Agent reactivity is high, and selectivity is high, stable in catalytic performance, and very high formic acid selectivity is maintained in very wide current range.
In existing electroreduction carbon dioxide system, the activation of water is promoted to will lead to the competition of carbon dioxide reduction reaction
Reaction, water restores the aggravation of evolving hydrogen reaction, to reduce the selectivity of carbon dioxide reduction.And the present invention passes through chalcogen
Doping, realizes the efficient activation of water, but does not significantly promote production hydrogen, maintains high carbon dioxide also while promoting water activation
Former selectivity, significantly improves the activity of formic acid processed.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph of the indium metal elctro-catalyst of 4.9% sulfur doping；
Fig. 2 is the nucleus magnetic hydrogen spectrum figure of carbon dioxide formic acid reaction product；
Fig. 3 is formic acid selectivity variation diagram of the indium metal of 4.9% sulfur doping under different current densities.
Specific embodiment
In order to be clearer and more clear technical problems, technical solutions and advantages to be solved, tie below
Drawings and examples are closed, the present invention is described in further details.
In the examples below, the compound mole of the simple substance of chalcogen or chalcogen can for 0~
0.4mmol；The mole of metal salt can be 0.4~3mmol, and the volume of DMF is 10~100mL.
Embodiment 1
First by 16 μm of ol thioacetamides and 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min, so
It is transferred in the stainless steel autoclave of 25mL polytetrafluoro liner afterwards, is put into clean 1 × 3cm2Carbon paper seals, at 150 DEG C of heating
Manage 12h；Carbon paper is taken out after cooling, and is washed with deionized, it is dry, obtain the S doping In of carbon paper load2O3Presoma；Finally
In 0.5M KHCO3The In gold for the 4.9mol%S doping that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to carbon paper
Belong to elctro-catalyst (S-In), as shown in Figure 1, the scanning electron microscope (SEM) photograph of the indium metal elctro-catalyst for 4.9% sulfur doping, sulfur doping
The partial size of indium metal is about 130nm, is equably supported on the carbon fiber of carbon paper.Cathode is done with the catalyst, Pt piece does anode,
Saturated calomel electrode does reference electrode, is reacted in H-type electrolytic cell, and cathode chamber and anode chamber are 30mL 0.5M
KHCO3Electrolyte；Carbon dioxide is with certain 20mL min-1Flow velocity is passed through in catholyte, application -0.98V potentiometric response
1h, formic acid generating rate are 1002 μm of ol h-1cm-2, faradic efficiency 93%.Fig. 2 is carbon dioxide formic acid reaction product
Nucleus magnetic hydrogen spectrum figure carry out quantifying for formic acid using dimethyl sulfoxide as internal standard.
As shown in figure 3, changing the current potential applied on S-In catalyst is -0.83~-1.23V vs.RHE, current density 25
~100mAcm-2, it is 85% or more that nucleus magnetic hydrogen spectrum quantitative analysis, which shows that formic acid faradic efficiency maintains,.
Embodiment 2
First by 16 μm of ol thioacetamides and 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min；So
It is transferred in the stainless steel autoclave of 25mL polytetrafluoro liner afterwards, is put into clean 1 × 3cm2Carbon paper seals, at 150 DEG C of heating
Manage 12h；Carbon paper is taken out after cooling, and is washed with deionized, it is dry, obtain the S doping In of carbon paper load2O3Presoma；Finally
In 0.5M KHCO3The In gold for the 4.9mol%S doping that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to carbon paper
Belong to elctro-catalyst (S-In).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；It is electrolysed in H-type
It is reacted in pond, cathode chamber and anode chamber are 30mL 0.5M CsHCO3Electrolyte；Carbon dioxide is with certain 20mL
min-1Flow velocity is passed through in catholyte, application -0.98V vs.RHE potentiometric response 1h；Current density is 84mAcm-2, nuclear-magnetism
Hydrogen spectrum quantitative analysis shows that formic acid faradic efficiency is 93%, and generating rate is 1449 μm of ol h-1cm-2。
Embodiment 3
First by 16 μm of ol thioacetamides and 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min；So
It is transferred in the stainless steel autoclave of 25mL polytetrafluoro liner afterwards, is put into clean 1 × 3cm2Carbon cloth seals, at 150 DEG C of heating
Manage 12h；Carbon cloth is taken out after cooling, and is washed with deionized, it is dry, obtain the S doping In of carbon cloth load2O3Presoma；Finally
In 0.5M KHCO3The In gold for the 4.9mol%S doping that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to carbon cloth
Belong to elctro-catalyst (S-In).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；It is electrolysed in H-type
It is reacted in pond, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with certain 20mL min-1Flow velocity is passed through in catholyte, application -0.98V vs.RHE potentiometric response 1h；Current density is 35mAcm-2, nucleus magnetic hydrogen spectrum
Quantitative analysis shows that formic acid faradic efficiency is 92%, and generating rate is 601 μm of ol h-1cm-2。
Embodiment 4
First by 16 μm of ol thioacetamides and 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min；So
It is transferred in the stainless steel autoclave of 25mL polytetrafluoro liner afterwards, is put into clean 1 × 3cm2Graphite flake, sealing, 150 DEG C of heating
Handle 12h；Graphite flake is taken out after cooling, and is washed with deionized, it is dry, obtain the S doping In of graphite flake load2O3Forerunner
Body；Finally in 0.5M KHCO3The 4.9mol%S that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to graphite flake mixes
Miscellaneous In metal elctro-catalyst (S-In).Cathode is done with the catalyst, graphite rod does anode, and saturated calomel electrode does reference electricity
Pole；It is reacted in H-type electrolytic cell, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with one
Fixed 20mL min-1Flow velocity is passed through in catholyte, application -0.98V vs.RHE potentiometric response 1h；Current density is 16mA
cm-2, nucleus magnetic hydrogen spectrum quantitative analysis show formic acid faradic efficiency be 88%, generating rate be 265 μm of ol h-1cm-2。
Embodiment 5
First by 16 μm of ol selenium powders and 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min；Then it shifts
Into the stainless steel autoclave of 25mL polytetrafluoro liner, it is put into clean 1 × 3cm2Carbon paper, sealing, 150 DEG C of heat treatment 12h；
Carbon paper is taken out after cooling, and is washed with deionized, it is dry, obtain the Se doping In of carbon paper load2O3Presoma；Finally exist
0.5M KHCO3The In metal elctro-catalyst for the Se doping that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to carbon paper
(Se-In).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；It is carried out in H-type electrolytic cell
Reaction, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with certain 20mLmin-1Flow velocity is passed through
In catholyte, application -0.98V vs.RHE potentiometric response 1h；Current density is 50mA cm-2, nucleus magnetic hydrogen spectrum quantitative analysis
Show that formic acid faradic efficiency is 90%, generating rate is 841 μm of ol h-1cm-2。
Embodiment 6
First by 16 μm of ol H2TeO4With 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min；Then turn
It moves in the stainless steel autoclave of 25mL polytetrafluoro liner, is put into clean 1 × 3cm2Carbon paper, sealing, 150 DEG C of heat treatment
12h；Carbon paper is taken out after cooling, and is washed with deionized, it is dry, obtain the Te doping In of carbon paper load2O3Presoma；Finally
In 0.5M KHCO3The In metal electro-catalysis for the Te doping that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to carbon paper
Agent (Te-In).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；In H-type electrolytic cell into
Row reaction, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with certain 20mLmin-1Flow velocity is logical
Enter in catholyte, application -0.98V vs.RHE potentiometric response 1h；Current density is 41mA cm-2, nucleus magnetic hydrogen spectrum quantitatively divides
Analysis shows that formic acid faradic efficiency is 89%, and generating rate is 676 μm of ol h-1cm-2。
Embodiment 7
First by 6 μm of ol thioacetamides and 20 μ L SnCl4It is dissolved in 12mL DMF, is vigorously stirred 15min；Then turn
It moves in the stainless steel autoclave of 15mL polytetrafluoro liner, is put into clean 1 × 3cm2Carbon paper, sealing, 180 DEG C of heat treatment
24h；Carbon paper is taken out after cooling, and is washed with deionized, it is dry, obtain the S doping SnO of carbon paper load2Presoma；Finally exist
0.5M KHCO3The Sn metal elctro-catalyst for the S doping that -1.23V vs.RHE electroreduction 5min loads in electrolyte up to carbon paper
(S-Sn).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；It is carried out in H-type electrolytic cell anti-
It answers, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with certain 20mLmin-1Flow velocity is passed through yin
In the electrolyte of pole, application -0.98V vs.RHE potentiometric response 1h；Current density is 43mA cm-2, nucleus magnetic hydrogen spectrum quantitative analysis table
Bright formic acid faradic efficiency is 81%, and generating rate is 640 μm of ol h-1cm-2。
Embodiment 8
First by 6 μm of ol thioacetamides and 0.2mmol BiCl3It is dissolved in 12mL DMF, is vigorously stirred 15min；Then
It is transferred in the stainless steel autoclave of 15mL polytetrafluoro liner, is put into clean 1 × 3cm2Carbon paper, sealing, 180 DEG C of heat treatment
24h；Carbon paper is taken out after cooling, and is washed with deionized, it is dry, obtain the S doping Bi of carbon paper load2O3Presoma；Finally exist
0.5M KHCO3The Bi metal elctro-catalyst for the S doping that -0.98V vs.RHE electroreduction 5min loads in electrolyte up to carbon paper
(S-Bi).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；It is carried out in H-type electrolytic cell anti-
It answers, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with certain 20mL min-1Flow velocity is passed through
In catholyte, application -0.98V vs.RHE potentiometric response 1h；Current density is 45mA cm-2, nucleus magnetic hydrogen spectrum quantitative analysis
Show that formic acid faradic efficiency is 92%, generating rate is 767 μm of ol h-1cm-2。
Comparative example 1
It is added without thioacetamide, by 0.4mmol InCl3It is dissolved in 15mL DMF, is vigorously stirred 15min；Then turn
It moves in the stainless steel autoclave of 25mL polytetrafluoro liner, is put into clean 1 × 3cm2Carbon paper, sealing, 150 DEG C of heat treatment
12h；Carbon paper is taken out after cooling, and is washed with deionized, and dry, obtain carbon paper load adulterates In without S2O3Presoma；Finally
In 0.5M KHCO3- 0.98V vs.RHE electroreduction 5min urges in electrolyte up to the In metal electricity without S doping that carbon paper loads
Agent (S0-In).Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electrode；In H-type electrolytic cell
It is reacted, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with certain 20mL min-1Stream
Speed is passed through in catholyte, application -0.98V potentiometric response 1h, and formic acid generating rate is 523 μm of ol h-1cm-2, faraday's effect
Rate is 93%.
Comparative example 2
Use business indium foil as catalyst.Cathode is done with the catalyst, Pt piece does anode, and saturated calomel electrode does reference electricity
Pole；It is reacted in H-type electrolytic cell, cathode chamber and anode chamber are 30mL 0.5M KHCO3Electrolyte；Carbon dioxide is with one
Fixed 20mL min-1Flow velocity is passed through in catholyte, application -0.98V potentiometric response 1h, and formic acid generating rate is 60 μm of olh-1cm-2, faradic efficiency 58%.
Embodiment 1 is compared with comparative example 1, and formic acid generating rate is 1002 μm of ol h in embodiment 1-1cm-2, it is identical anti-
2 times without sulfur doping 0mol%S0-In under the conditions of answering；Faradic efficiency is 93% in embodiment 1, is nothing under same reaction conditions
1.1 times of sulfur doping 0mol%S0-In.
Embodiment 1 is compared with comparative example 2, and formic acid generating rate is business indium foil under same reaction conditions in embodiment 1
17 times, faradic efficiency is 1.6 times of business indium foil under same reaction conditions in embodiment 1.
Claims (10)
1. the catalyst of electroreduction carbon dioxide formic acid, it is characterised in that: the catalyst is the metal of chalcogen doping
Elctro-catalyst, the chalcogen include at least one of sulphur, selenium and tellurium, the metal include in indium, tin, lead and bismuth extremely
Few one kind.
2. the catalyst of electroreduction carbon dioxide formic acid as described in claim 1, it is characterised in that: the content of chalcogen is rubbed
Your percentage is 0.01%~25%.
3. preparing the preparation method of the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 1 or 2, it is characterised in that:
The following steps are included:
1) first by the compound and dissolving metal salts of the simple substance of chalcogen or chalcogen in n,N-Dimethylformamide,
It is then placed in carbon material, is finally transferred in autoclave and carries out solvent heat treatment；
2) carbon material is taken out after solvent heat treatment, and is washed with deionized, and is dried to get carbon material supported sulfur family is arrived
The metal oxide precursor of element doping, the metal electro-catalysis that then electroreduction adulterates up to carbon material supported chalcogen
Agent.
4. the preparation method of the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 3, it is characterised in that: the carbon
Material includes at least one of carbon paper, carbon cloth, graphite flake, foamy carbon, carbon nanotube.
5. the preparation method of the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 4, it is characterised in that: the carbon
Material is carbon paper.
6. the preparation method of the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 3, it is characterised in that: the sulphur
The compound of race's element in sulphur powder, thiocarbamide, vulcanized sodium, thioacetamide, selenium powder, sodium selenite, tellurium powder, tellurous acid at least
It is a kind of.
7. the preparation method of the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 3, it is characterised in that: the gold
Belong to salt and is selected from least one of indium, tin, lead and chlorate, nitrate and the acetylacetonate of bismuth.
8. the preparation method of the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 3, it is characterised in that: solvent heat
The temperature of processing is 130~200 DEG C, and the time of solvent heat treatment is 12~48h, and it is -0.98V that electroreduction, which handles current potential,
vs.RHE。
9. the catalyst of the claim 1~8 electroreduction carbon dioxide formic acid is applied to electroreduction carbon dioxide first
In acid, it is characterised in that: reacted in H-type electrolytic cell, the metal elctro-catalyst of chalcogen doping does cathode, Pt piece or
Graphite does anode, and saturated calomel electrode does reference electrode, and carbon dioxide is passed through in catholyte, applies negative potential and carries out electricity
Solution, obtains formic acid.
10. the catalyst of electroreduction carbon dioxide formic acid as claimed in claim 9 is applied to electroreduction carbon dioxide formic acid
In, it is characterised in that: carbon dioxide flow rate is 5~100mL min-1；Electrolyte includes NaHCO3、KHCO3、CsHCO3And K2SO4
At least one of, concentration of electrolyte is 0.1~2M；Negative potential is -0.33~-1.23V vs.RHE.
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