CN110465290A - Ultra-thin palladium piece is promoting the application in carbon dioxide electroreduction - Google Patents
Ultra-thin palladium piece is promoting the application in carbon dioxide electroreduction Download PDFInfo
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- CN110465290A CN110465290A CN201810450188.8A CN201810450188A CN110465290A CN 110465290 A CN110465290 A CN 110465290A CN 201810450188 A CN201810450188 A CN 201810450188A CN 110465290 A CN110465290 A CN 110465290A
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- palladium
- carbon dioxide
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 177
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 79
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 35
- 230000001737 promoting effect Effects 0.000 title claims abstract description 9
- 230000000694 effects Effects 0.000 claims abstract description 12
- 229910052751 metal Inorganic materials 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 30
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 28
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 21
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 238000000034 method Methods 0.000 abstract description 12
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000003775 Density Functional Theory Methods 0.000 abstract description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 230000001603 reducing effect Effects 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract description 2
- 239000000377 silicon dioxide Substances 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000003795 desorption Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010931 gold Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 235000019441 ethanol Nutrition 0.000 description 4
- 230000005588 protonation Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical class Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- UXAMZEYKWGPDBI-UHFFFAOYSA-N C(CCCCCCCCCCCCCCC)Br(C)(C)C Chemical compound C(CCCCCCCCCCCCCCC)Br(C)(C)C UXAMZEYKWGPDBI-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses ultra-thin palladium piece and is promoting the application in carbon dioxide electroreduction, pass through solution thermal method, by the type, dosage and the reaction time that regulate and control reducing agent and surfactant, synthesize various sizes of regular hexagon palladium piece, count different loci ratio, experiment probes into the site source of activity promotion in conjunction with Density function theory.The growing method of the ultra-thin palladium nano sheet of hexagon in the present invention, easy to operate, reaction condition is mild, preparation process controllability, repeatability is strong, is not necessarily to large-scale instrument and equipment, economically feasible, while the material silica carbon reducing property prepared is superior, has certain industrial value.
Description
Technical field
The present invention relates to carbon dioxide electroreduction cathode fields, more particularly, specially utilize the side of ultra-thin palladium piece
Edge site, efficient catalytic carbon dioxide generates the application of carbon monoxide and mechanism is probed into.
Background technique
Carbon dioxide is the predominant gas for generating greenhouse effects, has caused serious weather and energy problem.Dioxy
Change carbon electroreduction be it is effective inhibit CO2 emission and produce high added value product a kind of effective ways (C.Costentin,
M.Robert,J.M.Saveant,Chem.Soc.Rev.2013,42,2423-2436).However, due to carbon dioxide reduction
Kinetic rate is slow, the dog-eat-dog from evolving hydrogen reaction, carbon dioxide conversion lock into always excessively high take-off potential and
Lower selectivity of product (J.Qiao, Y.Liu, F.Hong, J.Zhang, Chem.Soc.Rev.2014,43,631-675).Gold
Metal catalyst has obtained extensive concern and research in carbon dioxide electroreduction, because metal has fabulous electric conductivity, and
And metal the absorption of intermediate product * CO would be typically weaker than * H in evolving hydrogen reaction absorption (S.Liu, H.Tao, L.Zeng, Q.Liu,
Z.Xu,Q.Liu,J.L.Luo,J.Am.Chem.Soc.2017,139,2160-2163).Gold (W.Zhu, Y.J.Zhang,
H.Zhang,H.Lv,Q.Li,R.Michalsky,A.A.Peterson,S.Sun,J.Am.Chem.Soc.2014,136,
16132-16135), silver-colored (C.Kim, H.S.Jeon, T.Eom, M.S.Jee, H.Kim, C.M.Friend, B.K.Min,
Y.J.Hwang, J.Am.Chem.Soc.2015,137,13844-13850), palladium (D.Gao, H.Zhou, J.Wang, S.Miao,
F.Yang, G.Wang, J.Wang, X.Bao, J.Am.Chem.Soc.2015,137,4288-4291), zinc (H.Won da,
H.Shin,J.Koh,J.Chung,H.S.Lee,H.Kim,S.I.Woo,Angew.Chem.Int.Ed.2016,55,9297-
9300) good activity is shown in the reaction that carbon dioxide conversion generates carbon monoxide and formic acid.
The effective way for further effectively improving metallic catalyst performance is building low coordination site abundant.Because intermediate
The adsorption energy of product usually changes with the ligancy of reaction site, therefore the selectivity of different products also can occur to change accordingly
Become.Gold, silver, the Particle size of palladium, the metals such as copper have been proven that this point.Researchers are by seeking suitable metal partial size
To optimize overpotential and selectivity of product., by improved activity due in edge, the ratio in corner, the sites such as platform becomes for they
Change.In addition, probing into for related active site further demonstrates that, the low coordination site of part metals catalyst can effectively promote entirety
Electric current and selectivity of product.Compared with the metallic particles for only carrying out partial size optimization, nanowires of gold (W.Zhu, Y.J.Zhang,
H.Zhang,H.Lv,Q.Li,R.Michalsky,A.A.Peterson,S.Sun,J.Am.Chem.Soc.2014,136,
16132-16135) and Nano silver piece (S.Liu, H.Tao, L.Zeng, Q.Liu, Z.Xu, Q.Liu, J.L.Luo,
J.Am.Chem.Soc.2017,139,2160-2163) under the facilitation of edge site abundant, all realize lower
Beginning current potential and higher carbon monoxide selective.Noble metal gold, silver are analogous to, the edge site of palladium is also conducive to carbon monoxide production
It is raw.However, extremely limited for the research of palladium chtalyst generation carbon monoxide at present.So far, palladium-based catalyst is in carbon dioxide electricity
Reduction generate carbon monoxide peak efficiency be reach 91.2% under voltage compared to standard hydrogen electrode -0.89V (D.Gao,
H.Zhou,J.Wang,S.Miao,F.Yang,G.Wang,J.Wang,X.Bao,J.Am.Chem.Soc.2015,137,4288-
4291)。
Summary of the invention
It is an object of the invention to overcome the deficiencies of the prior art and provide ultra-thin palladium pieces in promoting carbon dioxide electroreduction
Application, the ultra-thin hexagon palladium piece surface of exhaustive rule, different ligancy sites to carbon dioxide electroreduction be an oxygen
Change the influence of carbon.
Technical purpose of the invention is achieved by following technical proposals:
Ultra-thin palladium piece is promoting the application in carbon dioxide electroreduction, using the small nano palladium slice of side length as catalyst,
With the low coordination site generated using catalyst edge, to promote the activity and selectivity of carbon dioxide electroreduction.
Moreover, increasing with palladium piece side length, the Metal Palladium atom of bulk and the metal of coordination 7-8 are coordinated in Metal Palladium atom
Palladium atom increases (i.e. body phase atomic ratio increases) as side length increases, and Metal Palladium of the coordination less than 5 is former in Metal Palladium atom
Son, coordination 5-6 Metal Palladium atom and be coordinated 6-7 Metal Palladium atom with side length increase and reduce (i.e. body phase atomic ratio subtracts
It is few).
It is preferred that the palladium piece that side length is 5.1nm is used as catalyst, it is coordinated the Metal Palladium atom less than 5 in Metal Palladium atom, matches
The Metal Palladium atom of position 5-6 and the Metal Palladium atom of coordination 6-7 reach maximum value, reach 94% carbon monoxide faradic efficiency
Only need the overpotential relative to standard hydrogen electrode -0.5V.
The present invention has the unsaturated coordination of more margin location using ultra-thin hexagon palladium piece, be conducive to carbon dioxide adsorption and
Protonation generates * COOH, effectively reduces the take-off potential of carbon monoxide generation, and effectively improves the selection of carbon monoxide
Property.The carbon monoxide faradic efficiency for reaching 94% only needs overpotential relative to standard hydrogen electrode -0.5V, compared to other
Palladium-based catalyst significantly reduces the maximized overpotential of carbon monoxide faradic efficiency.
Compared with prior art, Investigation of Metal Surface ligancy of the present invention influences catalytic activity, and the present invention mainly passes through
Solution thermal method is synthesized various sizes of regular by regulating and controlling type, dosage and the reaction time of reducing agent and surfactant
Hexagon palladium piece counts different loci ratio, tests in conjunction with Density function theory, and the site for probing into activity promotion is come
Source.The growing method of the ultra-thin palladium nano sheet of hexagon in the present invention, easy to operate, reaction condition is mild, preparation process controllability,
It is repeated strong, it is not necessarily to large-scale instrument and equipment, economically feasible.The material silica carbon reducing property of preparation is superior simultaneously, has one
Determine industrial value.Ultra-thin palladium piece rich in unsaturated edge site as a kind of efficient carbon dioxide electroreduction cathode material,
Overpotential is effectively reduced, promotes carbon monoxide faradic efficiency, performance surmounts most noble metal catalysts.It is expected to realize quotient
Industry carbon dioxide electroreduction, the problem that is effectively relieved that current greenhouse effects are serious, and environmental pollution is serious.
Detailed description of the invention
Fig. 1 is the schematic diagram of technical solution of the present invention.
Fig. 2 is the TEM photo of nano palladium slice catalyst used in the present invention.
Fig. 3 is the current density of different size nano palladium slice catalyst used in the present invention and carbon monoxide faraday effect
Rate test result curve graph (carbon dioxide Electrochemical Properties figure).
Fig. 4 is the carbon monoxide partial quality electric current signal of different size nano palladium slice catalyst used in the present invention
Figure.
Fig. 5 is the electric current and product selection schematic diagram of comparative catalyst's nanoparticle palladium in the present invention.
Fig. 6 is the electrochemistry effective area figure of nano palladium slice and nanoparticle palladium in the present invention.
Fig. 7 is the electrochemical impedance schematic diagram of nano palladium slice and nanoparticle palladium in the present invention.
Fig. 8 is the Ta Fuer slope test curve figure of catalyst in the present invention, carbon monoxide electrochemical desorption and reaction machine
Schematic diagram is released in understanding.
Fig. 9 is the ligancy calculating figure of nano palladium slice catalyst used in the present invention.
Figure 10 is that different ligancies and the corresponding curve diagram of atomic ratio be (i.e. in the nano palladium slice of different side lengths in the present invention
Active site count schematic diagram), wherein 1 be bulk, 2 be coordination 7-8,3 be coordination 5-6,4 be coordinated 6-7,5 be coordinated it is small
In 5.
Figure 11 is that side length is based in the present invention for five atoms, with a thickness of the Density function theory of five atomic layers
Figure.
Figure 12 is the conversion frequency figure of palladium piece catalyst in carbon dioxide reduction reaction of the present invention.
Specific embodiment
Technical solution of the present invention is further described below by specific embodiment.
The preparation that nano palladium slice is carried out according to existing literature passes through modulation material morphology and size, effectively control active sites
Point quantity, so that the method for clearly probing into effective active site and the promotion of titanium dioxide carbon dots reducing property, specifically as follows:
Embodiment 1. mixes palladium acetylacetonate, polyvinylpyrrolidone, sodium bromide, n,N-Dimethylformamide and water,
Purification 10 hours, gained homogeneous phase solution is transferred to glass container.Carbon monoxide is passed through to an atmospheric pressure, under 100 degrees Celsius
Heating, after be cooled to room temperature.Ethanol-acetone mixed solution centrifugation, obtain side length be 5.1 nanometers palladium piece (S.Tang,
M.Chen, N.Zheng, Small 2014,10,3139-3144), as follows:
(1) by 10mg palladium acetylacetonate, 32mg polyvinylpyrrolidone, 30.6mg sodium bromide and 2mL N, N- dimethyl methyl
Amide and the mixing of 4mL water, stand 10 hours, gained homogeneous phase solution is transferred to glass container.Carbon monoxide is passed through to an atmosphere
Pressure, heats 1 hour under 100 degrees Celsius, then cools to room temperature.
(2) 2mL acetone is added in products therefrom, is centrifuged 10 minutes under 10000rpm revolving speed.Obtained solid precipitating is centrifuged to add
Enter the mixture of 2mL ethyl alcohol and 4mL acetone, is centrifuged 2 times.Finally disperse solid precipitating in 2mL ethyl alcohol.
(3) 10mg ethyl alcohol, 100 μ L naphthol solutions, ultrasound 30 minutes are added into the 2mL ethyl alcohol of dispersion palladium piece.
(4) working electrode will be used as in the catalyst drop coating to glass-carbon electrode after ultrasound, platinized platinum is used as to electrode, silver/chlorine
Changing silver electrode is that reference electrode is assembled into electrochemical cell, carries out the test of carbon dioxide Electrochemical Properties.Electrolyte is 0.1M
KHCO3Solution, pH value 6.8, participation response area are 0.5cm2.Reaction product uses gas-chromatography on-line analysis.
2. palladium acetylacetonate of embodiment, citric acid, ten hexamethyl trimethylammonium bromides, polyvinylpyrrolidone, N, N- bis-
Methylformamide mixing, stands 1 hour.Gained homogeneous phase solution is transferred to flask, and tungsten carbonyl is added, anti-under argon atmosphere
It answers.Half an hour is reacted under 80 degrees Celsius.After being cooled to room temperature, centrifugation obtain side length be 9.6 nano palladium slices (Y.Li, W.Wang,
K.Xia,W.Zhang,Y.Jiang,Y.Zeng,H.Zhang,C.Jin,Z.Zhang,D.Yang,Small2015,11,4745-
4752)-reacted using 1 method of embodiment, difference is only that the reaction reagent replacement of step (1) are as follows: 16mg levulinic
Ketone palladium, 140mg citric acid, 60mg cetyl trimethylammonium bromide, 30mg polyvinylpyrrolidone, 100mg tungsten carbonyl,
10mL N,N-dimethylformamide.
3. palladium acetylacetonate of embodiment, citric acid, ten hexamethyl trimethylammonium bromides, polyvinylpyrrolidone, N, N- bis-
Methylformamide mixing, stands 1 hour.Gained homogeneous phase solution is transferred to flask, and tungsten carbonyl is added, anti-under argon atmosphere
It answers.It is reacted one hour under 80 degrees Celsius.After being cooled to room temperature, centrifugation obtain side length be 15.9 nano palladium slices (Y.Li, W.Wang,
K.Xia,W.Zhang,Y.Jiang,Y.Zeng,H.Zhang,C.Jin,Z.Zhang,D.Yang,Small 2015,11,4745-
4752)-reacted using 1 method of embodiment, difference is only that the reaction reagent replacement of step (1) are as follows: 16mg levulinic
Ketone palladium, 90mg citric acid, 60mg cetyl trimethylammonium bromide, 30mg polyvinylpyrrolidone, 100mg tungsten carbonyl,
10mL N,N-dimethylformamide.
4. palladium acetylacetonate of embodiment, polyvinylpyrrolidone, sodium bromide, n,N-Dimethylformamide and water mixing, it is quiet
It sets 10 hours.Gained homogeneous phase solution is transferred to flask, is passed through carbon monoxide to an atmospheric pressure, reaction 1 is small under 100 degrees Celsius
When.After being cooled to room temperature, centrifugation obtain side length be 23.2 nano palladium slices (X.Huang, S.Tang, X.Mu, Y.Dai, G.Chen,
Z.Zhou, F.Ruan, Z.Yang, N.Zheng, Nature nanotech 2011,6,28-32)-using 1 method of embodiment into
Row reaction, difference are only replaced in the reaction reagent of step (1) are as follows: 50mg palladium acetylacetonate, 185mg cetyl trimethyl bromination
Ammonium, 160mg polyvinylpyrrolidone, 10mL n,N-Dimethylformamide, 2mL water.
5. palladium acetylacetonate of embodiment, polyvinylpyrrolidone, cetyl trimethylammonium bromide, N, N- dimethyl formyl
Amine and water mixing.Gained homogeneous phase solution is transferred to flask, is passed through carbon monoxide to an atmospheric pressure, reaction 1 is small under 100 degrees Celsius
When.After being cooled to room temperature, centrifugation obtain side length be 52.6 nano palladium slices (X.Huang, S.Tang, X.Mu, Y.Dai, G.Chen,
Z.Zhou, F.Ruan, Z.Yang, N.Zheng, Nature nanotech 2011,6,28-32)-using 1 method of embodiment into
Row reaction, difference are only that the reaction reagent replacement of step (1) are as follows: 50mg palladium acetylacetonate, 185mg cetyl trimethyl bromine
Change ammonium, 160mg polyvinylpyrrolidone, 10mL n,N-Dimethylformamide, 2mL water.
As shown in Fig. 1, it is adsorbed using CO in (111) crystal face and chloride ion is in (100) crystal face suction-operated, synthesized super
Thin hexagon palladium piece；As shown in Fig. 2, scheme palladium piece side length statistics, about 5.1nm in (a)；(b) palladium piece is adsorbed on active carbon in
On, palladium piece can be obtained with a thickness of five atomic layers in meeting exposed side.
As shown in Fig. 3, curve 1,2,3,4,5 respectively represent side length be 5.1nm, 9.6nm, 15.9nm, 23.2nm,
The palladium piece of 52.6nm.The palladium piece of 5.1nm side length, overall current density is maximum, and carbon monoxide selective highest reaches in -0.5V
94% selectivity, after up to 8 hours stability tests, activity and selectivity does not all decline.The palladium of other side lengths
Piece, as side length increases, downward trend is presented in current density and selectivity.As shown in Fig. 4, curve 5,4,3,2,1 generations respectively
Table side length is 5.1nm, 9.6nm, 15.9nm, the palladium piece of 23.2nm, 52.6nm.As palladium piece side length increases, the list of carbon monoxide
The current density of position quality is gradually reduced.
As shown in attached drawing 5-7, nano palladium slice and palladium nano-particles are compared, compared with the palladium particle of diameter 5nm,
The palladium piece of side length 5.1nm shows great advantage on carbon monoxide selective；1,2 respectively represents 5.1nm palladium piece and 5nm
Grain, sheet palladium electrochemistry effective area are bigger；1,2 respectively represents 5nm particle and 5.1nm palladium piece, and sheet palladium impedance is smaller, more sharp
In the transmission of surface charge.
To probe into carbon dioxide electroreduction reaction mechanism, the experimentally measurement of Ta Fuer slope and an oxidation have been carried out first
The test of carbon electrochemical desorption, as shown in Fig. 8, the Ta Fuer slope (i.e. straight slope) of palladium piece increase with side length and are become larger, and say
The dynamics of bright carbon dioxide adsorption protonation process increases with side length and is slowed down；Palladium piece electrochemical desorption spectrogram as it can be seen that with
Side length increases, and the desorption peaks of carbon monoxide are mobile to low potential, shows that carbon monoxide desorption process reduces with palladium piece side length and become
It is easy；It is comprehensive to show that palladium piece side length reduces, while being conducive to carbon dioxide protonation and carbon monoxide desorption.
For the different loci for further discriminating between carbon dioxide electroreduction, in the palladium piece of different side lengths, each representativeness position
Point and its generalization ligancy are counted, and are distinguished according to ligancy is generalized to atomic species and its ratio.Such as
Shown in attached drawing 9-11, calculate the coordination situation of (Metal Palladium) atom first, then be respectively by ligancy " less than 5,5-6,6-7,
7-8, bulk " increase with palladium piece side length, the ratio variation of different ligancies and body phase atom, wherein coordination bulk and coordination 7-
8 increase as side length increases, remaining coordination increases with side length and reduced.It is five originals that Density function theory, which is based on side length,
Son has calculated separately palladium piece different loci with a thickness of half of palladium piece expansion of five atomic layers, carbon dioxide electro-reduction reaction
Free energy of reaction.The site DJ and FL, minimum energy needed for carbon dioxide protonates, and the test of Ta Fuer slope shows to side length
The smallest palladium piece, carbon dioxide protonation is rate constants, and therefore, DJ and FL are promoting the carbon dioxide electricity of 5.1nm palladium piece also
The most key effect is played in former activity.(carbon dioxide reduction activity figure) as shown in Fig. 12, it can be seen that side length
The palladium piece catalyst of 5.1nm shows best take-off potential and carbon monoxide faradic efficiency, reaches 94% carbon monoxide
Faradic efficiency only needs the overpotential of 500mV, lower than the palladium piece catalyst granules of other side lengths.To which explanation passes through control crystal
Growth, and the pattern and size of building nano particle, can promote carbon dioxide reduction catalytic performance.
Illustrative description has been done to the present invention above, it should explanation, the case where not departing from core of the invention
Under, any simple deformation, modification or other skilled in the art can not spend the equivalent replacement of creative work equal
Fall into protection scope of the present invention.
Claims (3)
1. ultra-thin palladium piece is promoting the application in carbon dioxide electroreduction, which is characterized in that made using the small nano palladium slice of side length
For catalyst, with the low coordination site generated using catalyst edge, to promote the activity and selectivity of carbon dioxide electroreduction.
2. ultra-thin palladium piece according to claim 1 is promoting the application in carbon dioxide electroreduction, which is characterized in that with palladium
Piece side length increases, and the Metal Palladium atom of bulk and the Metal Palladium atom of coordination 7-8 are coordinated in Metal Palladium atom as side length increases
And increase (i.e. body phase atomic ratio increases), the Metal Palladium of Metal Palladium atom of the coordination less than 5, coordination 5-6 in Metal Palladium atom
The Metal Palladium atom of atom and coordination 6-7 increase with side length and reduce (i.e. body phase atomic ratio is reduced).
3. ultra-thin palladium piece according to claim 1 is promoting the application in carbon dioxide electroreduction, which is characterized in that side length
For 5.1nm palladium piece as catalyst, Metal Palladium atom of the coordination less than 5 in Metal Palladium atom, the Metal Palladium atom for being coordinated 5-6
Reach maximum value with the Metal Palladium atom of coordination 6-7, reaches 94% carbon monoxide faradic efficiency and only need relative to standard
The overpotential of hydrogen electrode -0.5V.
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