CN110465290B - Application of ultrathin palladium sheet in promotion of carbon dioxide electroreduction - Google Patents
Application of ultrathin palladium sheet in promotion of carbon dioxide electroreduction Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 66
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 36
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 36
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 29
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 29
- 229910052751 metal Inorganic materials 0.000 claims description 23
- 239000002184 metal Substances 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 20
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- 230000001737 promoting effect Effects 0.000 claims description 3
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- 239000004094 surface-active agent Substances 0.000 abstract description 2
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 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 10
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- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
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- 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
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- 230000008569 process Effects 0.000 description 2
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- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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- 230000000052 comparative effect Effects 0.000 description 1
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- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
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- 238000004817 gas chromatography Methods 0.000 description 1
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- 125000000896 monocarboxylic acid group Chemical group 0.000 description 1
- 238000011056 performance test Methods 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
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
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- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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- 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
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Abstract
The invention discloses an application of an ultrathin palladium sheet in promotion of carbon dioxide electroreduction, which synthesizes regular hexagonal palladium sheets with different sizes by regulating the type, the dosage and the reaction time of a reducing agent and a surfactant through a solution thermal method, counts different site proportions, combines experiments with density functional theory calculation, and explores a site source with improved activity. The growth method of the hexagonal ultrathin palladium nanosheet is simple to operate, mild in reaction condition, controllable in preparation process, strong in repeatability, free of large-scale instruments and equipment, economical and feasible, and excellent in carbon dioxide reduction performance of the prepared material, and has a certain industrial value.
Description
Technical Field
The invention relates to the field of carbon dioxide electroreduction cathodes, in particular to application and mechanism exploration for efficiently catalyzing carbon dioxide to generate carbon monoxide by utilizing edge sites of an ultrathin palladium sheet.
Background
Carbon dioxide is the major gas producing the greenhouse effect and has caused serious climate and energy problems. Carbon dioxide electroreduction is an effective method for effectively suppressing carbon dioxide emission and producing high value-added products (c. costentin, m.robert, j.m.savant, chem.soc.rev.2013,42, 2423-. However, due to the slow kinetic rate of carbon dioxide reduction, the competition from hydrogen evolution reactions is intense and carbon dioxide conversion has been hampered by excessively high initial potentials and low product selectivities (J.Qiao, Y.Liu, F.hong, J.Zhang, chem.Soc.Rev.2014,43,631-. Metal catalysts have gained widespread interest and research in carbon dioxide electroreduction because metals have excellent electrical conductivity and the adsorption of CO to intermediates by metals is generally weaker than the adsorption of H in hydrogen evolution reactions (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 (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.Chem.Soc.137, Int.Zhou, H.4291-4291, zinc (H.4288-4291, H.4251, Woo.H.H.422015, Woo.H.H.H.4251, Woo.H.K.H.H.H.H.H.H.H.H.H.422015, Woo, H.H.H.H.H.H.H.H.4297, Woo H.H.H.H.H.H.H.J.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H.H..
An effective way to further effectively improve the performance of the metal catalyst is to construct abundant low coordination sites. Since the adsorption energy of the intermediate products is usually accompanied by a change in the coordination number of the reaction sites, the selectivity of the different products will therefore change accordingly. This has been demonstrated by the particle size effect of metals such as gold, silver, palladium, copper, etc. Researchers optimize overpotential and product selectivity by seeking appropriate metal particle sizes. They attribute improved activity to the change in the ratio of edge, corner, plateau, etc. sites. In addition, the research on the active sites further shows that the low coordination sites of part of the metal catalysts can effectively improve the overall current and the product selectivity. Compared with metal particles with optimized particle size, the gold nano-wire (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 the silver nano-sheet (S.Liu, H.Tao, L.Zeng, Q.Liu, Z.xu, Q.Liu, J.L.Luo, J.Am.Chem.Soc.2017,139,2160-2163) realize lower initial potential and higher carbon monoxide selectivity under the promotion action of abundant edge sites. The edge sites of palladium also favor carbon monoxide production, analogous to the noble metals gold and silver. However, the current research on palladium-catalyzed carbon monoxide production is very limited. To date, the highest efficiency of palladium-based catalysts for the electroreduction of carbon dioxide to carbon monoxide is 91.2% compared to the voltage of-0.89V for standard hydrogen electrodes (d.gao, h.zhou, j.wang, s.miao, f.yang, g.wang, j.wang, x.bao, j.am.chem.soc.2015,137, 4288-4291).
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the application of an ultrathin palladium sheet in promoting carbon dioxide electroreduction, and elaborates the influence of different coordination number sites on the electroreduction of carbon dioxide into carbon monoxide on the surface of the regular ultrathin hexagonal palladium sheet.
The technical purpose of the invention is realized by the following technical scheme:
the application of the ultrathin palladium sheet in promoting carbon dioxide electroreduction adopts a nano palladium sheet with small side length as a catalyst, and utilizes low coordination points generated at the edge of the catalyst to promote the activity and selectivity of carbon dioxide electroreduction.
Furthermore, as the side length of the palladium sheet increases, the metal palladium atom coordinated to bulk and the metal palladium atom coordinated to 7 to 8 in the metal palladium atom increase with the side length (i.e., the bulk atomic ratio increases), and the metal palladium atom coordinated to less than 5, the metal palladium atom coordinated to 5 to 6 and the metal palladium atom coordinated to 6 to 7 in the metal palladium atom decrease with the side length (i.e., the bulk atomic ratio decreases).
Preferably, a palladium sheet with a side length of 5.1nm is used as a catalyst, the metal palladium atom coordinated with less than 5, the metal palladium atom coordinated with 5-6 and the metal palladium atom coordinated with 6-7 in the metal palladium atoms reach the maximum, and the carbon monoxide faradaic efficiency reaching 94% only needs an overpotential of-0.5V relative to a standard hydrogen electrode.
The ultrathin hexagonal palladium sheet has unsaturated coordination with more edge positions, is beneficial to carbon dioxide adsorption and protonation to generate COOH, effectively reduces the initial potential generated by carbon monoxide, and effectively improves the selectivity of the carbon monoxide. Achieving 94% carbon monoxide faradaic efficiency requires only-0.5V overpotential relative to standard hydrogen electrodes, greatly reducing the overpotential at which carbon monoxide faradaic efficiency is maximized compared to other palladium-based catalysts.
Compared with the prior art, the influence of the coordination number of the metal surface on the catalytic activity is researched, regular hexagonal palladium sheets with different sizes are synthesized mainly by a solution thermal method through regulating the type, the dosage and the reaction time of a reducing agent and a surfactant, the proportion of different sites is counted, experiments are combined with density functional theory calculation, and the site source with improved activity is researched. The growth method of the hexagonal ultrathin palladium nanosheet is simple to operate, mild in reaction condition, controllable in preparation process, strong in repeatability, free of large-scale instruments and equipment, and economical and feasible. Meanwhile, the prepared material has excellent carbon dioxide reduction performance and certain industrial value. The ultrathin palladium sheet rich in unsaturated edge sites is used as a high-efficiency carbon dioxide electroreduction cathode material, so that the overpotential is effectively reduced, the Faraday efficiency of carbon monoxide is improved, and the performance of the ultrathin palladium sheet exceeds that of most noble metal catalysts. Is expected to realize commercial carbon dioxide electroreduction, and effectively relieves the problems of serious greenhouse effect and serious environmental pollution at present.
Drawings
FIG. 1 is a schematic diagram of the technical solution of the present invention.
FIG. 2 is a TEM photograph of the nano-palladium plate catalyst used in the present invention.
Fig. 3 is a graph showing the current density and faradaic efficiency test results of carbon monoxide (carbon dioxide electroreduction performance) for different sizes of nano-palladium plate catalysts used in the present invention.
FIG. 4 is a schematic of the mass current of carbon monoxide fraction for different size nano-palladium plate catalysts used in the present invention.
FIG. 5 is a schematic of the current and product selection for comparative catalyst nano-palladium particles in accordance with the present invention.
FIG. 6 is a diagram showing the electrochemically effective areas of the nano-palladium sheet and the nano-palladium particles according to the present invention.
Fig. 7 is a schematic diagram of electrochemical impedance of nano-palladium sheets and nano-palladium particles according to the present invention.
FIG. 8 is a graph of a Taverer slope test of the catalyst of the present invention, illustrating electrochemical desorption of carbon monoxide and reaction mechanism.
FIG. 9 is a graph showing the calculation of the coordination number of the nano-palladium sheet catalyst used in the present invention.
FIG. 10 is a corresponding graph (i.e. a statistical diagram of active sites) of different coordination numbers and atomic ratios in nano-palladium sheets with different side lengths according to the present invention, wherein 1 is bulk, 2 is coordination 7-8, 3 is coordination 5-6, 4 is coordination 6-7, and 5 is coordination less than 5.
FIG. 11 is a theoretical calculation chart based on a density functional of five atoms on a side and five atoms on a thickness in the present invention.
FIG. 12 is a graph showing the transition frequency of the palladium plate catalyst in the carbon dioxide reduction reaction according to the present invention.
Detailed Description
The technical solution of the present invention is further described in detail by the following specific examples.
The preparation of the nano palladium sheet is carried out according to the prior literature, the number of active sites is effectively controlled by modulating the shape and the size of the material, and thus the method for improving the reduction performance of the effective active sites and carbon dioxide points is clearly researched, and the method comprises the following steps:
example 1. palladium acetylacetonate, polyvinylpyrrolidone, sodium bromide, N-dimethylformamide and water were mixed, purified for 10 hours, and the resulting homogeneous solution was transferred to a glass vessel. Carbon monoxide was introduced to one atmosphere, heated at 100 ℃ and then cooled to room temperature. The ethanol-acetone mixed solution was centrifuged to obtain a palladium sheet (S.Tang, M.Chen, N.ZHEN, Small 2014,10, 3139-one 3144) with a side length of 5.1nm as follows:
(1) 10mg of palladium acetylacetonate, 32mg of polyvinylpyrrolidone, 30.6mg of sodium bromide were mixed with 2mL of N, N-dimethylformamide and 4mL of water, and left to stand for 10 hours, and the resulting homogeneous solution was transferred to a glass container. Carbon monoxide was introduced to one atmosphere, heated at 100 ℃ for 1 hour, and then cooled to room temperature.
(2) The resulting product was added to 2mL of acetone and centrifuged at 10000rpm for 10 minutes. The solid precipitate obtained by centrifugation was added with a mixture of 2mL of ethanol and 4mL of acetone and centrifuged 2 times. Finally, the solid precipitate was dispersed in 2mL of ethanol.
(3) To 2mL of ethanol in which the palladium sheet was dispersed, 10mg of ethanol and 100. mu.L of a naphthol solution were added, and the mixture was sonicated for 30 minutes.
(4) Dripping the catalyst after ultrasonic treatment on a glassy carbon electrode to serve as a working electrode, and taking a platinum sheet as a working electrodeAnd assembling an electrochemical cell by taking the silver/silver chloride electrode as a reference electrode as a counter electrode, and carrying out carbon dioxide electroreduction performance test. The electrolyte is 0.1M KHCO3The pH value of the solution is 6.8, and the participating reaction area is 0.5cm2. The reaction product was analyzed on-line by gas chromatography.
Example 2 palladium acetylacetonate, citric acid, cetyltrimethylammonium bromide, polyvinylpyrrolidone, N-dimethylformamide were mixed and left to stand for 1 hour. Transferring the obtained homogeneous solution to a flask, adding tungsten hexacarbonyl, and reacting under the atmosphere of argon. Reacting for half an hour at 80 ℃. After cooling to room temperature, centrifugation yielded palladium sheets with side lengths of 9.6nm (Y.Li, W.Wang, K.Xia, W.Zhang, Y.Jiang, Y.Zeng, H.Zhang, C.jin, Z.Zhang, D.Yang, Small2015,11, 4745. one 4752) -reacted using the procedure of example 1, with the only difference that the reagents of step (1) were replaced with: 16mg of palladium acetylacetonate, 140mg of citric acid, 60mg of cetyltrimethylammonium bromide, 30mg of polyvinylpyrrolidone, 100mg of tungsten hexacarbonyl, 10mL of N, N-dimethylformamide.
Example 3 palladium acetylacetonate, citric acid, cetyltrimethylammonium bromide, polyvinylpyrrolidone, N-dimethylformamide were mixed and left to stand for 1 hour. Transferring the obtained homogeneous solution to a flask, adding tungsten hexacarbonyl, and reacting under the atmosphere of argon. The reaction was carried out at 80 ℃ for one hour. After cooling to room temperature, centrifugation yielded palladium sheets with side lengths of 15.9nm (Y.Li, W.Wang, K.Xia, W.Zhang, Y.Jiang, Y.Zeng, H.Zhang, C.jin, Z.Zhang, D.Yang, Small2015,11, 4745. one 4752) -reacted using the procedure of example 1, with the only difference that the reagents of step (1) were replaced with: 16mg of palladium acetylacetonate, 90mg of citric acid, 60mg of cetyltrimethylammonium bromide, 30mg of polyvinylpyrrolidone, 100mg of tungsten hexacarbonyl, 10mL of N, N-dimethylformamide.
Example 4 palladium acetylacetonate, polyvinylpyrrolidone, sodium bromide, N-dimethylformamide and water were mixed and left to stand for 10 hours. The resulting homogeneous solution was transferred to a flask and carbon monoxide was introduced to one atmosphere and reacted at 100 ℃ for 1 hour. After cooling to room temperature, centrifugation yielded palladium flakes with a side length of 23.2nm (x.huang, s.tang, x.mu, y.dai, g.chen, z.zhou, f.ruan, z.yang, n.zheng, Nature nanotech 2011,6,28-32) -reactions were carried out using the method of example 1, except that the reaction reagents in step (1) were replaced with: 50mg of palladium acetylacetonate, 185mg of cetyltrimethylammonium bromide, 160mg of polyvinylpyrrolidone, 10mL of N, N-dimethylformamide, 2mL of water.
Example 5 palladium acetylacetonate, polyvinylpyrrolidone, cetyltrimethylammonium bromide, N-dimethylformamide and water were mixed. The resulting homogeneous solution was transferred to a flask and carbon monoxide was introduced to one atmosphere and reacted at 100 ℃ for 1 hour. After cooling to room temperature, centrifugation yielded palladium plates with side lengths of 52.6nm (x.huang, s.tang, x.mu, y.dai, g.chen, z.zhou, f.ruan, z.yang, n.zheng, Nature nanotech 2011,6,28-32) -reactions were carried out using the method of example 1, except that the reaction reagents of step (1) were replaced with: 50mg of palladium acetylacetonate, 185mg of cetyltrimethylammonium bromide, 160mg of polyvinylpyrrolidone, 10mL of N, N-dimethylformamide, 2mL of water.
As shown in attached figure 1, an ultrathin hexagonal palladium sheet is synthesized by utilizing the adsorption of CO on a (111) crystal face and the adsorption of chloride ions on a (100) crystal face; as shown in FIG. 2, the side length of the palladium sheet in the graph (a) is about 5.1 nm; (b) the middle palladium sheet is adsorbed on the active carbon, and the side surface is exposed, so that the thickness of the palladium sheet is five atomic layers.
As shown in FIG. 3, curves 1, 2, 3,4, and 5 represent palladium plates with sides of 5.1nm, 9.6nm, 15.9nm, 23.2nm, and 52.6nm, respectively. The palladium sheet with the side length of 5.1nm has the largest total current density and the highest carbon monoxide selectivity, reaches 94 percent of selectivity at minus 0.5V, and does not reduce the activity and the selectivity after a stability test for 8 hours. Other side length palladium sheets show a decreasing trend in current density and selectivity as the side length increases. As shown in FIG. 4, curves 5, 4, 3, 2, 1 represent palladium plates with sides of 5.1nm, 9.6nm, 15.9nm, 23.2nm, and 52.6nm, respectively. As the side length of the palladium sheet increases, the current density per unit mass of carbon monoxide gradually decreases.
As shown in fig. 5-7, comparing the pd nanoplates with pd nanoparticles, the pd nanoplates with sides of 5.1nm show a great advantage in carbon monoxide selectivity compared to pd nanoparticles with a diameter of 5 nm; 1 and 2 respectively represent a 5.1nm palladium sheet and a 5nm particle, and the electrochemical effective area of the sheet palladium is larger; 1 and 2 respectively represent 5nm particles and 5.1nm palladium sheets, and the sheet palladium has smaller impedance and is more beneficial to the transmission of surface charges.
In order to explore the carbon dioxide electroreduction reaction mechanism, firstly, the experimental determination of the taffer slope and the carbon monoxide electrochemical desorption test are carried out, as shown in the attached figure 8, the taffer slope (namely the straight slope) of the palladium sheet is increased along with the increase of the edge length, which shows the dynamics of the carbon dioxide adsorption protonation process and slows down along with the increase of the edge length; the electrochemical desorption spectrogram of the palladium sheet can be seen, and the desorption peak of the carbon monoxide moves to a low potential along with the increase of the side length, which shows that the carbon monoxide desorption process has easy capacity change along with the decrease of the side length of the palladium sheet; the synthesis shows that the side length of the palladium sheet is reduced, and carbon dioxide protonation and carbon monoxide desorption are facilitated.
In order to further distinguish different sites of carbon dioxide electroreduction, statistics is carried out on each representative site and the generalized coordination number thereof in palladium sheets with different side lengths, and atomic species and proportions thereof are distinguished according to the generalized coordination number. As shown in the attached figures 9-11, firstly, the coordination condition of the (metal palladium) atom is checked, and then the coordination numbers are respectively less than 5, 5-6, 6-7, 7-8 and bulk, as the side length of the palladium sheet is increased, the proportions of different coordination numbers and bulk atoms are changed, wherein the coordination bulk and the coordination 7-8 are increased as the side length is increased, and the rest coordination is reduced as the side length is increased. The density functional theory calculation is based on the development of a half palladium sheet with the side length of five atoms and the thickness of five atoms, and the reaction free energy of carbon dioxide electroreduction reaction at different sites of the palladium sheet is calculated respectively. And the energy required by carbon dioxide protonation is the lowest at DJ and FL sites, and a tower Verer slope test shows that the carbon dioxide protonation is a speed control step for the palladium sheet with the smallest edge length, so DJ and FL play the most critical role in improving the carbon dioxide electroreduction activity of the palladium sheet with the 5.1 nm. As shown in FIG. 12 (carbon dioxide reduction activity diagram), it can be seen that the palladium plate catalyst with 5.1nm side length exhibits the best initial potential and carbon monoxide faradaic efficiency, and only 500mV overpotential is needed to reach 94% of carbon monoxide faradaic efficiency, which is lower than the other side length palladium plate catalyst particles. Therefore, the carbon dioxide reduction catalytic performance can be improved by controlling the crystal growth and constructing the shape and the size of the nano particles.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (1)
1. The application of the ultrathin palladium sheet in promoting carbon dioxide electroreduction is characterized in that a palladium sheet with the side length of 5.1nm is used as a catalyst, a metal palladium atom with coordination less than 5, a metal palladium atom with coordination 5-6 and a metal palladium atom with coordination 6-7 in the metal palladium atoms reach the maximum value, and the faradaic efficiency of carbon monoxide reaching 94% only needs an overpotential of-0.5V relative to a standard hydrogen electrode.
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| CN101817090A (en) * | 2010-04-23 | 2010-09-01 | 厦门大学 | Synthesis method of palladium nano sheet |
| KR20160071198A (en) * | 2014-12-11 | 2016-06-21 | 서강대학교산학협력단 | Preparation method for palladium nanoparticles |
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| CN101817090A (en) * | 2010-04-23 | 2010-09-01 | 厦门大学 | Synthesis method of palladium nano sheet |
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| JP2017177094A (en) * | 2016-03-28 | 2017-10-05 | 古河電気工業株式会社 | Metal-containing nanoparticle-carrying catalyst and carbon dioxide reduction apparatus |
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