CN109096341A - A kind of complex, preparation method and the catalyst for applying the complex - Google Patents

A kind of complex, preparation method and the catalyst for applying the complex Download PDF

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CN109096341A
CN109096341A CN201811042364.0A CN201811042364A CN109096341A CN 109096341 A CN109096341 A CN 109096341A CN 201811042364 A CN201811042364 A CN 201811042364A CN 109096341 A CN109096341 A CN 109096341A
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complex
solution
melon
catalyst
cyclics
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陈茹茹
曹敏纳
李红芳
曹荣
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Fujian Institute of Research on the Structure of Matter of CAS
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Fujian Institute of Research on the Structure of Matter of CAS
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Priority to CN201910520819.3A priority patent/CN110066299B/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
    • C07F15/0086—Platinum compounds
    • C07F15/0093—Platinum compounds without a metal-carbon linkage
    • 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
    • C25B1/00—Electrolytic production of inorganic compounds or non-metals
    • 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
    • C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
    • C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
    • C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
    • C25B11/095—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds at least one of the compounds being organic
    • 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
    • C25B3/23—Oxidation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

Abstract

This application discloses a kind of complexs, have chemical formula shown in Formulas I: L2 (H3O)·[PdCl4]·xH2O Formulas I；Wherein, L represents melon cyclics molecule；X represents the molal quantity of free water in every mole of complex, 6≤x≤8；The complex belongs to monoclinic system, I2/c space group, and cell parameter is

Description

A kind of complex, preparation method and the catalyst for applying the complex
Technical field
This application involves a kind of carbon dioxide reduction cathod catalysts and its preparation method and application, belong to electro-catalysis technology Field.
Background technique
Carbon dioxide generally arises from the breathing under natural situation and the mankind as one kind important in greenhouse gases Production activity in.Meanwhile for many industrial productions and tellurian plant, carbon dioxide is a kind of extremely important Raw material.In ideal conditions, the carbon dioxide generated on the earth and consumption should reach a balance.However, with change Carbon dioxide caused by stone fuel is continuously increased.The balance of carbon dioxide is gradually broken.Therefore, we will be from source On head reduce carbon dioxide discharge and by carbon dioxide conversion be useful substance.
Electro-catalysis be exactly it is such a under mild reaction conditions, carbon dioxide one-step is converted into an oxidation The method of the high-valued product and liquid fuel such as carbon, hydrocarbon and methanol.But the reduction of carbon dioxide electro-catalysis simultaneously is also deposited Reaction overpotential is higher and reaction process in the competitive reaction of hydrogen lead to the low challenge of selectivity of product.Therefore, It finds a kind of efficient catalyst and realizes that small overpotential and higher selectivity and stability are critically important.
Summary of the invention
According to the one aspect of the application, a kind of complex, preparation method, the dioxy for applying the complex are provided Change carbon reduction cathod catalyst and preparation method thereof, which is effectively reducing carbon dioxide reduction reaction overpotential Meanwhile improving catalyst choice and stability.Method for preparing catalyst is simple, and selectivity and stability are high.
The complex has chemical formula shown in Formulas I:
L·2(H3O)·[PdCl4]·xH2O Formulas I
Wherein, L represents melon cyclics molecule；
X represents the molal quantity of free water in every mole of complex, 6≤x≤8；
The complex belongs to monoclinic system, I2/c space group, and cell parameter is α=γ=90 °, β=94.9~95.0 °, Z=4.
Optionally, in the complex crystal, in every mole of complex comprising one mole in melon annular space chamber free water and Six moles of free water, every mole of complex contain one mole of melon ring outside melon ring.
In the complex crystal of the application, the cavity center of melon ring contains hydrone, is raw during forming crystal At.The melon annular space chamber of original addition does not simultaneously contain hydrone.
Optionally, the melon cyclics molecule is selected from five yuan of melon cyclics molecules, hexa-atomic melon cyclics At least one of molecule.
Optionally, the melon cyclics molecule is five yuan of melon rings of decamethyl.
Optionally, the chemical formula of the complex is [Me10CB[5]@H2O]·2H3O·[PdCl4]·6H2O, monoclinic crystal System, I2/c space group, α=γ= 90 °, β=94.97~94.98 °, Z=4.
Optionally, the chemical formula of the complex is [Me10CB[5]@H2O]·2H3O·[PdCl4]·6H2O, monoclinic crystal System, I2/c space group, α=γ=90 °, β= 94.9976 °, Z=4.
The complex is brown crystal.
According to the another aspect of the application, a kind of preparation method of complex is provided, this method is easy to operate, and yield is high.
The preparation method of the complex, which is characterized in that with the solution I containing palladium chloride and contain melon ring class chemical combination The solution II of object is raw material, is prepared into the complex using solution diffusion method.
It optionally, further include aqueous hydrochloric acid solution in the solution I containing palladium chloride.
Optionally, the solution diffusion method uses H-type diffuser, and diffusion time is no less than 3 hours；
The concentration of palladium chloride is 0.001mol/L~0.017mol/L in solution I；
Contain hydrogen ion in solution I, hydrionic concentration is 0.025mol/L~0.035mol/L；
The concentration of melon cyclics is 0.001mol/L~0.010mol/L in solution II.
Optionally, in solution I the concentration of palladium chloride the upper limit be selected from 0.002mol/L, 0.003mol/L, 0.004mol/L, 0.005mol/L、0.006mol/L、0.007mol/L、0.008mol/L、0.009mol/L、0.010mol/L、0.011mol/L、 0.012mol/L, 0.013mol/L, 0.014mol/L, 0.015mol/L, 0.016mol/L or 0.017mol/L；Chlorine in solution I Change palladium concentration lower limit be selected from 0.001mol/L, 0.002mol/L, 0.003mol/L, 0.004mol/L, 0.005mol/L, 0.006mol/L、0.007mol/L、0.008mol/L、0.009mol/L、0.010mol/L、0.011mol/L、0.012mol/L、 0.013mol/L, 0.014mol/L, 0.015mol/L or 0.016mol/L.
Optionally, in solution I hydrionic concentration the upper limit be selected from 0.026mol/L, 0.027mol/L, 0.028mol/L, 0.029mol/L, 0.030mol/L, 0.031mol/L, 0.032mol/L, 0.033mol/L, 0.034mol/L or 0.035mol/ L；In solution I the lower limit of hydrionic concentration be selected from 0.025mol/L, 0.026mol/L, 0.027mol/L, 0.028mol/L, 0.029mol/L, 0.030mol/L, 0.031mol/L, 0.032mol/L, 0.033mol/L or 0.034mol/L.
Optionally, in solution II the concentration of melon cyclics the upper limit be selected from 0.002mol/L, 0.003mol/L, 0.004mol/L, 0.005mol/L, 0.006mol/L, 0.007mol/L, 0.008mol/L, 0.009mol/L or 0.010mol/ L；In solution II the lower limit of the concentration of melon cyclics be selected from 0.001mol/L, 0.002mol/L, 0.003mol/L, 0.004mol/L, 0.005mol/L, 0.006mol/L, 0.007mol/L, 0.008mol/L or 0.009mol/L.
Those skilled in the art according to specific needs, select suitable crystallization time.Preferably, the solution diffusion method Using H-type diffuser, diffusion time is no less than 3 hours.Selectively, the range lower limit of diffusion time be selected from 3 hours, 5 hours, 10 hours, 15 hours, 20 hours, 2 days, 3 days.It is further preferred that the diffusion time is 3 hours~20 days.Further Preferably, the diffusion time is 3 hours~14 days.After diffusion time being more than 14 days, there is stray crystal generation.
Optionally, which comprises
(1) deionized water is added into palladium chloride and hydrochloric acid forms the transparent aqueous solution of palladium chloride, ie in solution I；
(2) under agitation, by Me10CB [5] dissolves in deionized water, obtains solution II；
(3) solution I and solution II are transferred to the side of reaction unit respectively, spreads, obtains the complex.
Optionally, the dosage of palladium chloride is 0.17mmol in solution I, and the dosage of 6M hydrochloric acid solution is 1ml, deionized water Dosage is 20ml.
Optionally, Me in solution II10The dosage of CB [5] is 0.1mmol, and the dosage of deionized water is 20ml.
As a kind of specific embodiment, the preparation method of the complex includes:
(1) deionized water is added into palladium chloride and hydrochloric acid forms the glassy yelloe aqueous solution (solution I) of palladium chloride.
(2) under magnetic stirring by Me10CB [5] dissolves in deionized water (solution II).
(3) solution I and II is carefully transferred to every side of H pipe respectively.In H pipe, after slowly spreading three days Obtain brown crystal.
According to the application's in another aspect, providing a kind of nano material, which is characterized in that the nano material is complex It is obtained after reduction；The complex in the complex, the complex being prepared according to the method at least one Kind.
The nano material is the Technique of Nano Pd of melon ring package.
Optionally, the Application of micron is in electro-catalysis carbon dioxide reduction reaction.
Optionally, the restoring method of the complex includes: 250~350 DEG C and hydrogenates 1~10 hour.
Optionally, the complex is the crystal grown up to by diffusion method；The complex is reduced to hydrogen for divalent Pd is slowly restored, and during reduction, weakens nano Pd particle using the confinement of hydrogen bond and melon ring in Supramolecular Assembling Reunion, more fully play it to CO2The catalytic performance of RR.
Optionally, the upper limit of the temperature of the hydrogenation be selected from 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C, 340 DEG C or 350 DEG C；The lower limit of the temperature of the hydrogenation is selected from 250 DEG C, 260 DEG C, 270 DEG C, 280 DEG C, 290 DEG C, 300 DEG C, 310 DEG C, 320 DEG C, 330 DEG C or 340 DEG C.
Optionally, the upper limit of the time of the hydrogenation is selected from 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 Hour, 9 hours or 10 hours；The lower limit of the time of the hydrogenation be selected from 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, it is 6 small When, 7 hours, 8 hours or 9 hours.
Optionally, the restoring method of the complex include: by complex in a hydrogen atmosphere, 250~350 DEG C heating 1 ~10 hours, obtain the nano material；
Wherein, the composition of the hydrogen atmosphere are as follows: the nitrogen that the hydrogen and volume fraction that volume fraction is 5% are 95%.
Optionally, the preparation method of the nano material includes after grinding complex, being passed through (+95% nitrogen of 5% hydrogen Gas), 250~350 DEG C are heated 1~10 hour, and reduction obtains the nano material；
The complex is selected from least one of the complex, complex that the method is prepared.
Optionally, the preparation method of the nano material after grinding complex, is passed through (+95% nitrogen of 5% hydrogen), 300 DEG C are heated 3 hours, and reduction obtains nano material.
As one kind, specifically embodiment, the preparation method of the nano material include: after grinding complex, to be put in In triangle furnace, it is passed through 5% hydrogen (95% is nitrogen) reduction, setting temperature is 300 DEG C, and the time is 3h required to get arriving Nano material.
According to the another aspect of the application, provide a kind of catalyst, which is characterized in that the catalyst include complex also What original obtained, the Technique of Nano Pd of melon ring package；The complex that the complex is selected from the complex, the method is prepared At least one of.
Optionally, the preparation method of the catalyst, comprising: restore the complex to obtain the Technique of Nano Pd of melon ring package Material；The nano palladium material that the melon ring wraps up is mixed with carboplatin carbon, obtains mixture I；Mixture I is added to containing different In the mixed solution I of propyl alcohol and water, Nafion solution is then added, ultrasonic mixing is uniform, obtains mixed solution I I, i.e., described to urge Agent；
Wherein, the volume ratio of isopropanol and water is 1:1 in mixed solution I；The volume ratio of mixed solution I and Nafion solution For 300~200:1.
Optionally, the nano palladium material of the melon ring package and the mass ratio of carboplatin carbon are 1:1.
Optionally, mixed solution I and the volume ratio of Nafion solution are 250:1.
As a kind of specifically embodiment, the preparation method of the catalyst, comprising the following steps:
1, complex is obtained into the nano palladium material of melon ring package with hydrogen reducing；
2, the nano palladium material being supported on melon ring and carboplatin carbon are put into the same vial, solution isopropyl is added Alcohol, water, nafion, ultrasound；
3, the liquid for being dispersed with material that will be obtained drips on carbon paper, as electrode, carries out electrochemical property test.
As a kind of specific embodiment, the preparation method of the catalyst includes:
The nano palladium material that reduction obtains is mixed with carboplatin carbon, isopropanol is put in: in water=1:1 mixed solution, adding Enter Nafion solution ultrasound to be uniformly mixed.Carbon dioxide reduction elctro-catalyst can be obtained, i.e., the described catalyst.
As an implementation, the material, using five yuan of melon rings of decamethyl as ligand, is made using palladium chloride as presoma For PdMe10CB [5] complex after being restored with hydrogen, obtains the nano palladium material of melon ring package.
The preparation method of the catalyst, includes the following steps:
(1) ligand of the five yuan of melon rings of decamethyl as Supramolecular Assembling is synthesized first；
(2) deionized water (20ml) is added into palladium chloride (0.17mmol), the aqueous hydrochloric acid solution 1ml of 6M is added, formed The glassy yelloe aqueous solution (solution I) of palladium chloride；
(3) under magnetic stirring by Me10CB [5] (100mg, 0.1mmol) is dissolved in deionized water (20ml), forms nothing Color transparent aqueous solution (solution II)；
(4) solution I and II is carefully transferred to every side of H pipe respectively.By being slowly diffused in H pipe, after three days Obtain brown crystal；
(5) obtained crystal is ground, different temperature and times is selected to be hydrogenated in triangle furnace；Performance is optimal Condition is the 3h at 300 DEG C；
(6) it by the material after hydro-reduction, is mixed with carboplatin carbon according to the mass ratio of 1:1, in isopropanol: water=1:1 In mixed solution ultrasound to be uniformly mixed.Up to the catalyst.
According to the another aspect of the application, catalyst described in one kind is provided as carbon dioxide reduction cathod catalyst Using.
In the application, Me indicates methyl；CB [n] indicates melon cyclics, as CB [5] indicate five yuan of melon rings, CB [6] table Show hexa-atomic melon ring, Me10CB [5] indicates five yuan of melon rings of decamethyl；Me4CB [6] indicates Symmetric tetramethyl cucurbituril.
The beneficial effect that the application can generate includes:
(1) diffusion method synthetic crystal is utilized in the application, synthetic method is simple.The crystal structure degree of generation is high, in air Middle stabilization.
(2) utilize 5% hydrogen reducing crystal, reduction rate is slow, prevent nano particle because formation speed comparatively fast caused by Reunion.
(3) in reduction process, the hydrogen bond in crystal reduces the reunion of Technique of Nano Pd, meanwhile, the carbonyl of melon ring is due to slightly Negatively charged is incorporated in the surface of positively charged Technique of Nano Pd by electrostatic interaction, weakens the reunion of nano particle.Therefore, it obtains Material granule it is uniform, active site sufficiently expose.
(4) the catalyst Pd@Me prepared by the present invention10The selectivity of CB [5] is excellent, especially in lesser current potential -0.6V Vs.RHE (opposite reversible hydrogen electrode) shows high carbon monoxide selective, close to 90%.The cost of catalyst is reduced, together When improve the utilization rate of precious metals pd.
(5) the catalyst Pd@Me prepared by the present invention10The high stability of CB [5], it is highest in carbon monoxide selective Current potential (- 0.6V vs.RHE) carries out stability test 9h, and current efficiency remains original 91%.
(6) catalyst provides certain experience and reference for the research of carbon dioxide new catalyst.
Detailed description of the invention
Fig. 1 is PdMe prepared by embodiment 110The crystal structure figure of CB [5].
Fig. 2 is the TEM figure of Pd nano material prepared by embodiment 3, and wherein a is 300 DEG C, the Pd hydrogenated under the conditions of 3h The TEM of nano material schemes, and b is the high resolution TEM figure of Pd nano material, and the FFT that illustration is polycrystalline Pd schemes.
Fig. 3 is Pd@Me prepared by embodiment 510The carbon monoxide faradic efficiency figure of CB [5] catalyst.
Fig. 4 is Pd@Me prepared by embodiment 510The carbon monoxide current density figure of CB [5] catalyst.
Fig. 5 is Pd@Me prepared by embodiment 510The stability of CB [5] catalyst 9h at current potential (- 0.6V vs.RHE) is surveyed Examination.
Specific embodiment
The application is described in detail below with reference to embodiment, but the application is not limited to these embodiments.
Unless otherwise instructed, the raw material in embodiments herein and catalyst are bought by commercial sources, wherein chlorine Change palladium and is purchased from traditional Chinese medicines company；
Five yuan of melon ring Me of decamethyl10CB [5] is synthesized according to document, and poly methanol and 2 in synthesis material, 3- diacetyl is purchased From alfa company.Bibliography: Li H, L ü J, Lin J, et al.Crystalline Hybrid Solid Materials of Palladium and Decamethylcucurbit[5]uril as Recoverable Precatalysts for Heck Cross‐Coupling Reactions[J].Chemistry-A European Journal,2013,19(46): 15661-15668.
Concentrated hydrochloric acid, ethyl alcohol and acetone are purchased from Shanghai traditional Chinese medicines.
Analysis method is as follows in embodiments herein:
The instrument of chemical property and electrochemical stability test are as follows: Zahner IM6, for model for IM6, producer is moral State Zahner (Zha Na).
The instrument of catalyst stability test is Zahner IM6, and model IM6, producer is Germany Zahner (Zha Na).
The morphology characterization instrument of catalyst are as follows: Flied emission transmission electron microscope FEI Tecnai G2F20, model FEI Tecnai G2F20, producer are FEI Co. of the U.S..
The growing method of 1 crystal of embodiment
(1) deionized water (20ml) is added into palladium chloride (0.17mmol), the hydrochloric acid solution 1ml of 6M forms palladium chloride Transparent aqueous solution (solution I).Under magnetic stirring by Me10CB [5] (100mg, 0.1mmol) is dissolved in deionized water (20ml) (solution II).Solution I and II is carefully transferred to every side of H pipe respectively.In H pipe, by slowly spreading (standing) three It, obtains brown crystal.
(2) obtained crystal is washed with deionized 3 times, spontaneously dries obtain PdMe in air10CB [5] crystal. It is denoted as sample 1#, wherein the content of Pd is 9.86wt%.
2 crystallographic structural analysis of embodiment
The above X-ray single crystal diffraction data are collected under 100K using Super Nova CCD single crystal diffractometer, right Sample 1#Carry out structure elucidation.Diffraction light sources are graphite monochromatised Mo-K alpha rayScanning mode is ω-2θ；Data carry out absorption correction processing using Multi-Scan method.All calculating and refine use SHELXTL-97 program Packet is completed；The position that heavy atom is determined with direct method obtains remaining atomic coordinates with poor Fourier synthetic method；With based on F2It is complete The coordinate and anisotropy thermal parameter of all atoms of Matrix least square method refine.
Monocrystalline test result is as shown in Table 1 and Table 2.
Table 1
2 sample 1 of table#Atomic coordinates (not hydrogen atoms)
The crystal structure (being free of H) of sample 1# is as shown in Figure 1.
As seen from Figure 1, in sample 1#, free water by Hydrogenbond at the both ends of five yuan of melon rings of decamethyl, it is adjacent Molecular capsule pass through hydrogen bond and PdCl4 2-Form one-dimensional catenary structure.Hydrogen ion plays the role of balancing charge.
The preparation method of 3 nanometer Pd material of embodiment
The crystal PdMe that will be obtained10CB [5], is placed in quartz ampoule, is placed in triangle furnace, is passed through 5% hydrogen reducing (atmosphere The hydrogen for being 5% for volume fraction, the nitrogen that volume fraction is 95%).It is 300 DEG C that triangle furnace temperature, which is arranged, and the reaction time is 3h.The Technique of Nano Pd being supported on melon ring can be obtained.It is named as D-1#。
The morphology characterization of 4 nanometer Pd material of embodiment
The nanometer Pd material sample D-1 for the reduction that embodiment 3 is prepared#Carry out morphology characterization, sample D-1#TEM figure As shown in Figure 2 a and 2 b.Fig. 2 a shows that nanometer Pd material is spherical in uniform graininess, and partial size is in 2.2nm or so；Fig. 2 b is logical The High-Resolution Map for crossing calculating Technique of Nano Pd shows that spacing of lattice is 0.22nm, (111) face of corresponding Technique of Nano Pd.Illustration is Technique of Nano Pd Fourier transformation image, show the polycrystalline structure of Technique of Nano Pd, it is consistent with Pd (111) planar orientation.
The preparation method of 5 palladium nanocatalyst of embodiment
(1) Technique of Nano Pd (D-1 for obtaining reduction#) mixed with the carboplatin carbon of phase homogenous quantities, it is dispersed in 1ml ultrapure water and different In the mixed liquor of propyl alcohol (volume ratio 1:1), the naphthols nafion solution of 40 μ L, ultrasonic 2h are added.Doping carboplatin can be obtained The nano Pd catalyst of carbon.It is named as D-2#。
The preparation of 6 electrode of embodiment
(1) working electrode: take the mixing drop of the nano Pd catalyst of the doping carboplatin carbon in 240 μ L embodiments 5 in carbon Paper surface (area 1*1cm2), it is dry to get；
(2) platinum guaze is to electrode, reference electrode Ag/AgCl.Final load Metal Palladium in the catalyst of electrode surface Content be 120 μ g/cm2。
The test of 7 electro-chemical activity of embodiment
First in CO2Cyclic voltammetry scan, scanning speed 100mVs are carried out in 0.5M potassium bicarbonate solution under atmosphere-1, scanning range is -1.2~0V vs.RHE (opposite reversible hydrogen electrode), and 10 circle of scanning, the effect of the step is to catalyst table It is cleaned and plays certain activation in face.Then constant voltage test is carried out, gas-chromatography (GC) detects product,1HNMR Liquid product is detected, for DMSO as internal standard, it is Ag/AgCl electrode that the above scanning range, which chooses reference electrode, and Pt net is to electrode.
Fig. 3 to Fig. 5 is catalyst, i.e. sample D-2 provided by embodiment 5#Electrochemical property test figure.It can from figure To find out that catalyst synthesized by the application possesses higher selectivity, stability and catalytic activity.
During the test, hydrogen and carbon monoxide are only detected.Fig. 3 is sample D-2#Pd@Me10CB [5] catalyst produces The faradic efficiency figure of object, it can be seen that the material shows a high oxidation at lower current potential (- 0.6V vs.RHE) Carbon faradic efficiency, close to 90%, with the raising of overpotential, the competitive reaction of hydrogen, the faraday for leading to carbon monoxide is imitated Rate reduces.And required for lower overpotential is exactly us.
Fig. 4 is sample D-2#Pd@Me10The product current density figure of CB [5] catalyst.As can be seen that with overpotential It increases, the current density of carbon monoxide and hydrogen increases, and at current potential (- 1.1V vs.RHE), the current density of carbon monoxide is 2 times of hydrogen current density.
The test of 8 electrochemical stability of embodiment
Fig. 5 is sample D-2#Pd@Me10The stability test of CB [5] catalyst 9h at current potential (- 0.6V vs.RHE), figure 5 displays, after reaction carries out 9h, relative current densities can also remain original 91%, show higher stability.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, a little variation or modification are made using the technology contents of the disclosure above and is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (10)

1. a kind of complex, which is characterized in that the complex has chemical formula shown in Formulas I:
L·2(H3O)·[PdCl4]·xH2O Formulas I
Wherein, L represents melon cyclics molecule；
X represents the molal quantity of free water in every mole of complex, 6≤x≤8；
The complex belongs to monoclinic system, I2/c space group, and cell parameter is α=γ=90 °, β=94.9~95.0 °, Z=4.
2. complex according to claim 1, which is characterized in that the melon cyclics molecule is selected from five yuan of melon ring classes At least one of compound molecule, hexa-atomic melon cyclics molecule.
3. complex according to claim 1, which is characterized in that the chemical formula of the complex is [Me10CB[5]@ H2O]·2H3O·[PdCl4]·6H2O, monoclinic system, I2/c space group, α=γ=90 °, β=94.97~94.98 °, Z=4.
4. the preparation method of the described in any item complexs of claims 1 to 3, which is characterized in that with the solution I containing palladium chloride It is raw material with the solution II containing melon cyclics, the complex is prepared into using solution diffusion method.
5. according to the method described in claim 4, it is characterized in that, the solution diffusion method uses H-type diffuser, diffusion time No less than 3 hours；
Contain hydrogen ion in solution I, hydrionic concentration is 0.025mol/L~0.035mol/L；
The concentration of palladium chloride is 0.001mol/L~0.017mol/L in solution I；
The concentration of melon cyclics is 0.001mol/L~0.010mol/L in solution II.
6. according to the method described in claim 4, it is characterized in that, which comprises
(1) deionized water is added into palladium chloride and hydrochloric acid forms the transparent aqueous solution of palladium chloride, ie in solution I；
(2) under agitation, by Me10CB [5] dissolves in deionized water, obtains solution II；
(3) solution I and solution II are transferred to the side of reaction unit respectively, spreads, obtains the complex.
7. a kind of nano material, which is characterized in that the nano material is to obtain after complex restores；The complex is selected from power Benefit requires 1 to 3 described in any item complexs, in the complex being prepared according to any one of claim 4 to 6 the method At least one.
8. nano material according to claim 7, which is characterized in that the restoring method of the complex includes: 250~ 350 DEG C hydrogenate 1~10 hour；
Preferably, the restoring method of the complex includes: that 250~350 DEG C of heating 1~10 are small in a hydrogen atmosphere by complex When, obtain the nano material；
Wherein, the composition of the hydrogen atmosphere are as follows: the nitrogen that the hydrogen and volume fraction that volume fraction is 5% are 95%.
9. a kind of catalyst, which is characterized in that the catalyst includes obtaining after complex restores, the nanometer of melon ring package Palladium；The complex is selected from any one of the described in any item complexs of claims 1 to 3, claim 4 to 6 the method system Standby obtained at least one of complex.
10. catalyst as claimed in claim 9 is as carbon dioxide reduction cathod catalyst.
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