CN110066299A - 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 PDFInfo
- Publication number
- CN110066299A CN110066299A CN201910520819.3A CN201910520819A CN110066299A CN 110066299 A CN110066299 A CN 110066299A CN 201910520819 A CN201910520819 A CN 201910520819A CN 110066299 A CN110066299 A CN 110066299A
- Authority
- CN
- China
- Prior art keywords
- complex
- solution
- melon
- catalyst
- cyclics
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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, cell parameter
Description
Technical field
This application involves a kind of carbon dioxide reduction cathod catalysts and its preparation method and application, belong to electrochemical catalysis
Technical 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.But there is also anti-for the reduction of carbon dioxide electro-catalysis simultaneously
Answer overpotential higher and reaction process in the competitive reaction of hydrogen lead to the low challenge of the selectivity of product.Therefore, one is found
The efficient catalyst of kind 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/a space group, and cell parameter is α=γ=90 °, β=95.0~95.1 °, 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 of the application, the cavity center of melon ring contains hydrone, is generated during forming crystal.
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 [(H3O)2(Me10CB[5]@H2O)]·[PdCl4]·3H2O, monocline
Crystallographic system, I2/a space group, α
=γ=90 °, β=95.10~95.11 °, Z=4.
Optionally, the chemical formula of the complex is [(H3O)2(Me10CB[5]@H2O)]·[PdCl4]·3H2O, monocline
Crystallographic system, I2/a space group, α=γ=90 °, β=
95.1030 °, 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 two sides 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 are carefully transferred to the two sides of H pipe respectively.In H pipe, by being obtained 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 palladium nano-particles being supported on melon ring.
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 restores 1~10 hour.
Optionally, the complex is the crystal grown up to by diffusion method；The hydrogen that is reduced to of the complex will
[PdCl4]2-Slowly reduction.During reduction, hydrogen bond abundant in Supramolecular Assembling and the confinement effect of melon ring are utilized
Weaken the reunion of Pd nano particle, more fully plays it to CO2The catalytic performance of RR.
Optionally, the upper limit of the hydrogenation temperature is 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 be 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),
It 300 DEG C, heats 3 hours, 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 3 hours required to get arriving
The nano material wanted.
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 palladium nano-particles being supported on melon ring；The complex is selected from the complex, the method is prepared
At least one of complex.
Optionally, the preparation method of the catalyst, comprising: restore the complex to obtain the palladium being supported on melon ring
Nano particle；The palladium nano-particles being supported on melon ring are mixed with carboplatin carbon, obtain mixture I；Mixture I is added
Into the mixed solution I containing isopropanol and water, naphthol solution is then added, ultrasonic mixing is uniform, obtains mixed solution I I, i.e.,
The catalyst；
Wherein, the volume ratio of isopropanol and water is 1:1 in mixed solution I, and the volume ratio of mixed solution I and naphthol solution is
300~200:1.
Optionally, the mass ratio of the palladium nano-particles being supported on melon ring and carboplatin carbon is 1:1.
Optionally, the volume ratio of mixed solution I and naphthol solution is 250:1.
As a kind of specifically embodiment, the preparation method of the catalyst, comprising the following steps:
1, complex is obtained into the palladium nano-particles being supported on melon ring with hydrogen reducing；
2, the palladium nano-particles being supported on melon ring and carboplatin carbon are put into the same vial, isopropanol are added,
Water, naphthol solution, ultrasound；
3, the finely dispersed solution 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 nanometer Pd material that reduction obtains is mixed with carboplatin carbon, isopropanol is put in: in water=1:1 mixed solution, adding
Enter naphthol 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 PdCl4-Me10CB [5] complex, after being restored with hydrogen, obtains the palladium nano-particles being supported on melon ring.
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 are 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 at 300 DEG C, 3 hours；
(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 used in the application, synthetic method is simple.The crystal purity of generation is high, steady in air
It is fixed.
(2) 5% hydrogen reducing crystal is utilized, reduction rate is slow, effective that nano particle is inhibited comparatively fast to make because generating
At reunion.
(3) in reduction process, the hydrogen bond in crystal reduces the reunion of palladium nano-particles, meanwhile, the carbonyl of melon ring by
In slightly elecrtonegativity, it is incorporated in positively charged palladium nano-particles surface by electrostatic interaction, reduces the group of nano particle
It is poly-.Therefore, the palladium nano-particles obtained, partial size small (2.4nm) and it is uniform.
(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) (RHE: reversible hydrogen electrode) shows high carbon monoxide selective, faradic efficiency 92.5%.In -1.0V
(vs.RHE), the current density of carbon monoxide is 17.91mA/cm2.While catalyst performance improves, effectively raise expensive
The utilization rate of metal 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) is carried out stability test 12 hours, the carbon monoxide current density and faradic efficiency base of catalyst
Originally it remains unchanged.
(6) present invention provides a kind of new thinking for the design of nanocatalyst.
Detailed description of the invention
Fig. 1 is PdCl prepared by embodiment 14-Me10The crystal structure figure of CB [5].
Fig. 2 is the transmission electron microscope picture of Pd nano material prepared by embodiment 3；Wherein (a) is 300 DEG C, and 3 small hydrogenate at present
The TEM of the Pd nano material arrived schemes, and illustration is the grain size distribution of Pd nano particle；It (b) is the high-resolution of Pd nano material
Transmission electron microscope picture, illustration are selective electron diffraction figure.
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 510CB [5] catalyst 12 hours stabilizations at current potential -0.6V (vs.RHE)
Property test chart.
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.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: Shanghai Chen Hua CHI600E electrochemical workstation, model
For CHI600E, producer is Shanghai Chen Hua.
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., 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 are carefully transferred to the two sides of H pipe respectively.In H pipe, by slowly spreading (standing) three days, obtain
Obtain brown crystal.
(2) obtained crystal is washed with deionized 3 times, spontaneously dries obtain PdCl in air4-Me10CB [5] is brilliant
Body.It is denoted as sample 1#, wherein the mass 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 SuperNova CCD single crystal diffractometer, right
Sample 1# carries out structure elucidation.Diffraction light sources are graphite monochromatised Mo/K alpha rayScanning mode
For ω -2 θ；Data carry out absorption correction processing using Multi-Scan method.All calculating and refine use SHELXTL-97 journey
Sequence 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 F2's
The coordinate and anisotropy thermal parameter of all atoms of complete matrix least square method refine.
Monocrystalline test result is as shown in Table 1 and Table 2.Table 1 is the crystal data and refined parameters of sample 1#, and table 2 is sample
The atomic coordinates (not hydrogen atoms) of 1#.
Table 1: sample 1#Crystal data and refined parameters
Table 2: sample 1#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#, hydrogen ion by Hydrogenbond at the both ends of five yuan of melon rings of decamethyl,
Closed molecular capsule is formed, adjacent molecular capsule passes through hydrogen bond and [PdCl4]2-In conjunction with formation one-dimensional catenary structure.Hydration
Hydrogen ion plays the role of balancing charge.
The preparation method of 3 nanometer Pd material of embodiment
The crystal PdCl that will be obtained4-Me10CB [5], is placed in quartz ampoule, is placed in triangle furnace, is passed through hydrogen (5% hydrogen
+ 95% nitrogen) reduction.It is 300 DEG C that triangle furnace temperature, which is arranged, and the reaction time is 3 hours.It can be obtained and be supported on melon ring
Palladium nano-particles.It is named as D-1#。
The morphology characterization of 4 nanometer Pd material of embodiment
The sample D-1 that embodiment 3 is prepared#Carry out morphology characterization, sample D-1#TEM figure such as Fig. 2 (a) and Fig. 2 (b)
It is shown.Fig. 2 (a) display, nanometer Pd material is spherical in uniform graininess, and partial size is in 2.4nm or so；Fig. 2 (b) is palladium nanometer
The High-Resolution Map of grain, spacing of lattice 0.22nm, Pd (111) face (JCPDS no.46- of corresponding face-centred cubic structure
1043).Illustration is the selection electron diffraction diagram of palladium nano-particles, shows the weaker crystallinity of palladium nano-particles.
The preparation method of 5 palladium nanocatalyst of embodiment
(1) palladium nano-particles (D-1 for obtaining reduction#) mixed with the carboplatin carbon of 1/2 mass, it is dispersed in 1mL ultrapure water
In the mixed liquor of isopropanol (volume ratio 1:1), the naphthol solution of 40 μ L, ultrasound 2 hours are added.Doping carboplatin can be obtained
The palladium 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 120 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 CO2The KHCO of 0.5M under atmosphere3Cyclic voltammetry scan, scanning speed 100mVs are carried out in solution-1,
Scanning range is -1.2~0V (vs.RHE), and 10 circle of scanning, the effect of the step is that catalyst surface is cleaned and played
Certain activation.Then constant voltage test is carried out, gas-chromatography (GC) detects gas-phase product, and ion chromatography (IC) detects liquid
Phase product, it is reference electrode that the above scanning range, which chooses Ag/AgCl 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 carbon monoxide selective, activity and stability.
Fig. 3 is sample D-2#Pd-Me10The faradic efficiency figure of CB [5] catalyst product.Gas-phase product be carbon monoxide and
Hydrogen, liquid product are formic acid.In general, apply current potential and be lower than -0.6V (vs.RHE), the carbon monoxide method of palladium-based catalyst
Efficiency is drawn to can reach 85%.For the material in lower current potential -0.5V (vs.RHE), carbon monoxide faradic efficiency is i.e. up to
86%, illustrate that the catalyst possesses high carbon monoxide selective in lower overpotential.Especially, in -0.6V
(vs.RHE) when, the faradic efficiency of carbon monoxide reaches 92.5%, has been more than most of palladium-based catalysts under the current potential
Selectivity.In addition, the faradic efficiency of carbon monoxide is all 80% or more within the scope of entire test potential.Illustrate the catalysis
The higher carbon monoxide selective of agent.
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, increased trend is all presented in the current density of carbon monoxide, hydrogen and formic acid.Wherein, the current density of carbon monoxide increases
Add trend to be apparently higher than formic acid and carbon monoxide, illustrate the raising with overpotential, the generating rate of carbon monoxide accelerates.
The test of 8 electrochemical stability of embodiment
Fig. 5 is sample D-2#Pd-Me10CB [5] catalyst 12 hours stability at current potential -0.6V (vs.RHE) is surveyed
Examination, Fig. 5 show that after reaction carries out 12 hours, the faradic efficiency and current density of carbon monoxide all do not fail significantly, card
The bright higher stability of the catalyst.
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]·xH2Wherein, L represents melon cyclics molecule to O Formulas I；
X represents the molal quantity of free water in every mole of complex, 6≤x≤8；
The complex belongs to monoclinic system, I2/a space group, and cell parameter is α=γ=90 °, β=95.0~95.1 °, 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/a space group, α=γ=90 °, β=95.0~
95.1 °, 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 two sides 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~
It 350 DEG C, hydrogenates 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, and is supported on receiving on melon ring
Rice 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
At least one of complex being prepared.
10. catalyst as claimed in claim 9 is as carbon dioxide reduction cathod catalyst.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2018110423640 | 2018-09-07 | ||
| CN201811042364.0A CN109096341A (en) | 2018-09-07 | 2018-09-07 | A kind of complex, preparation method and the catalyst for applying the complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110066299A true CN110066299A (en) | 2019-07-30 |
| CN110066299B CN110066299B (en) | 2020-08-28 |
Family
ID=64865459
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811042364.0A Withdrawn CN109096341A (en) | 2018-09-07 | 2018-09-07 | A kind of complex, preparation method and the catalyst for applying the complex |
| CN201910520819.3A Active CN110066299B (en) | 2018-09-07 | 2019-06-17 | Complex, preparation method thereof and catalyst using complex |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811042364.0A Withdrawn CN109096341A (en) | 2018-09-07 | 2018-09-07 | A kind of complex, preparation method and the catalyst for applying the complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN109096341A (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110746610A (en) * | 2019-10-29 | 2020-02-04 | 贵州大学 | [ PdnClm]2Construction of induced cucurbituril supramolecular rigid framework materials |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040265237A1 (en) * | 2001-09-18 | 2004-12-30 | Kimoon Kim | Inclusion compound comprising cucurbituril derivatives as host molecule and pharmaceutical composition comprising the same |
| US20130004885A1 (en) * | 2011-06-29 | 2013-01-03 | Dusan Strmcnik | Fuel cell electrodes |
| CN103351409A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Hexahydric cucurbit urils based polar porous material and synthetic method thereof |
| CN103594718A (en) * | 2013-11-25 | 2014-02-19 | 中国科学院福建物质结构研究所 | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles |
| CN104368389A (en) * | 2014-12-07 | 2015-02-25 | 中国科学院福建物质结构研究所 | Supermolecule crystal material based platinum nano-catalyst and preparation and application thereof |
| CN107313066A (en) * | 2017-07-24 | 2017-11-03 | 中国科学院福建物质结构研究所 | Supported catalyst and its preparation method and application |
-
2018
- 2018-09-07 CN CN201811042364.0A patent/CN109096341A/en not_active Withdrawn
-
2019
- 2019-06-17 CN CN201910520819.3A patent/CN110066299B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040265237A1 (en) * | 2001-09-18 | 2004-12-30 | Kimoon Kim | Inclusion compound comprising cucurbituril derivatives as host molecule and pharmaceutical composition comprising the same |
| US20130004885A1 (en) * | 2011-06-29 | 2013-01-03 | Dusan Strmcnik | Fuel cell electrodes |
| CN103351409A (en) * | 2013-07-30 | 2013-10-16 | 贵州大学 | Hexahydric cucurbit urils based polar porous material and synthetic method thereof |
| CN103594718A (en) * | 2013-11-25 | 2014-02-19 | 中国科学院福建物质结构研究所 | Preparation and usage of nanoribbon-shaped Cucurbit[6]uril carried cubic palladium nanoparticles |
| CN104368389A (en) * | 2014-12-07 | 2015-02-25 | 中国科学院福建物质结构研究所 | Supermolecule crystal material based platinum nano-catalyst and preparation and application thereof |
| CN107313066A (en) * | 2017-07-24 | 2017-11-03 | 中国科学院福建物质结构研究所 | Supported catalyst and its preparation method and application |
Non-Patent Citations (5)
| Title |
|---|
| DUNFENG GAO等: "Size-Dependent Electrocatalytic Reduction of CO2 over Pd Nanoparticles", 《JOURANL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| FARAH BENYETTOU 等: "Palladium-Loaded Cucurbit[7]uril-Modified Iron Oxide Nanoparticles for C-C Cross-Coupling Reactions", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
| MINNA CAO等: "Platinum Nanoparticles Stabilized by Cucurbit[6]uril with Enhanced", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| SEKHAR NANDI等: "Cucurbit[6]uril-Stabilized Palladium Nanoparticles as a Highly Active Catalyst for Chemoselective Hydrogenation of Various Reducible Groups in Aqueous Media", 《CHEMISTRY SELECT》 * |
| 肖昕等: "十甲基五元瓜环与几种金属离子配合物的晶体结构", 《无机化学学报》 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110066299B (en) | 2020-08-28 |
| CN109096341A (en) | 2018-12-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111036261A (en) | Supported monatomic metal catalyst and preparation method and application thereof | |
| CN107486233B (en) | A kind of carbonitride adulterates the preparation method and application of carbon-based cobalt/cobalt oxide nanocatalyst | |
| CN111682223A (en) | Preparation of in-situ synthesized nitrogen-doped carbon sheet supported (Co, Ni, Fe) nanoparticle electrocatalyst | |
| CN112647095B (en) | Atomically dispersed bimetallic site anchored nitrogen-doped carbon material and preparation and application thereof | |
| CN110694666B (en) | C 3 N 4 @CeO 2 Supported low-content gold catalyst and preparation method and application thereof | |
| CN111229215A (en) | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof | |
| CN110227474B (en) | LaCoO with oxygen vacancy3Preparation method and application of nano material | |
| CN106000443A (en) | Method for preparing efficient and stable methane dry-reforming catalyst by means of one-step synthesis | |
| CN109175347A (en) | A kind of Au-Ir Nanoalloy, preparation method and the application as catalyst | |
| CN105789639A (en) | Method for preparing Au-cluster/carbon nano tube composite catalyst | |
| CN108611657A (en) | A kind of synthesis and application of the carbon nano-fiber electrochemical catalyst of nitrogenous cobalt molybdenum | |
| CN107029724B (en) | A kind of preparation method with CO modified with reduction reformation hydrogen production cobalt-base catalyst | |
| CN110066299A (en) | A kind of complex, preparation method and the catalyst for applying the complex | |
| CN110433815A (en) | A kind of carbon dioxide methanation nickel-base catalyst and its preparation method and application | |
| CN106807382A (en) | A kind of preparation method of high dispersive Ni/C catalyst | |
| CN114471658A (en) | Temperature-controlled bifunctional atomic-level dispersed metal g-C3N4Method for preparing photocatalyst | |
| CN114345368A (en) | PdCo bimetallic catalyst, preparation method and application thereof | |
| CN109499602A (en) | A kind of synthetic method of systematization regulation loading type iron elementide atom number | |
| CN104707603A (en) | Pt-PbOx/C catalyst and preparation method thereof | |
| CN111437820B (en) | Composite nano material for producing hydrogen by photocatalytic water decomposition and preparation method thereof | |
| CN101562250A (en) | Method for preparing cathode catalyst of proton exchange membrane fuel cell | |
| CN101249958B (en) | Method for continuous synthesis of a great amount of high specific surface area highly-graphitized carbon nano-cage by bubbling process | |
| CN114045524B (en) | Iridium monoatomic catalyst, preparation method and application thereof | |
| CN106669736B (en) | A kind of its application to nitroaromatic reduction of the preparation method of the magnetic kaolin nanocatalyst of carried noble metal alloy | |
| CN109638305A (en) | A kind of CuNCo with anti-perovskite structure3Type electro-catalysis oxygen-separating catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |