CN108187750A - A kind of ruthenium water oxidation catalyst based on elecrtonegativity ligand and preparation method thereof - Google Patents
A kind of ruthenium water oxidation catalyst based on elecrtonegativity ligand and preparation method thereof Download PDFInfo
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Abstract
A kind of ruthenium water oxidation catalyst based on elecrtonegativity ligand and preparation method thereof belongs to the technical field of catalyst preparation.Since elecrtonegativity ligand can reduce the overpotential of molecular catalyst, therefore we, which design, has synthesized an elecrtonegativity tridentate ligand with conjugated system, Long carbon chain is introduced in molecular catalyst again simultaneously so that it can which the multi-walled carbon nanotube with carboxylated is preferably combined.Therefore, which shows preferable chemical property in electro-catalysis water oxygen, and so as to which this catalyst provides effective half-reaction for water oxygen, a kind of effective approach is provided to solve environmental problem and energy problem.
Description
Technical field
The present invention relates to a kind of ruthenium water oxidation catalysts based on elecrtonegativity ligand and preparation method thereof, belong to catalyst
The technical field of preparation.
Background technology
Water oxygen chemoattractant molecule catalyst is quickly grown in recent years, and one of advantage is exactly that can change catalysis by adjusting ligand
The electrochemical properties of agent.The introducing of electronegative ligands advantageously reduces the potential energy of high-valence state reaction intermediate, can effectively reduce
The overpotential of catalyst accelerates the progress of water oxidation reaction.But current research distance really realizes that artificial photosynthesis also have
Very big gap, and electro-chemical water oxidized molecules device can improve the practical application of water oxygen chemoattractant molecule catalyst.Manual simulation's light
The final goal of cooperation is Hydrogen Energy to be converted solar energy into or other chemical energy that can directly utilize.To realize this mesh
, it is necessary to the photoelectrochemical cell of water decomposition is built, it is non-by being transferred to the research of water oxidation catalyst by homogeneous chemistry method
Homogeneous electrode surface, so as to fulfill the full decomposition reaction of water.
According to the document reported, three kinds can be divided into about method of modifying of the molecular catalyst in electrode surface：Physics
Absorption, covalent bond modification, non-covalent bond modification.Wherein, the electrode of physisorphtion modification, catalyst lacks with electrode surface to be tied
With joint efforts, cause electrode stability prepared by this method very poor, molecular catalyst easily comes off from electrode surface；And covalent bond is repaiied
Decorations method carries out complicated cumbersome modification reaction due to needing to molecular catalyst and electrode surface, significantly limits the method
Practical application.In recent years, the electrode prepared using non-covalent bond method of modifying, since its preparation process is relatively easy and has
Certain stability achieves breakthrough progress in terms of electro-chemical water decomposition.
2012, the method that Sun Li uses electrophoretic deposition into seminar, by the multi-walled carbon nanotube of carboxylated
(MWCNTsCOOH) ITO conductive glass surfaces are deposited to, select the catalyst [Ru through big conjugation group pyrene modificationII(bda)(Py-
py)2] and MWCNTsCOOH by pi-pi accumulation effect be combined, be prepared for composite electro catalytic water oxygen polarizing electrode.This catalysis electrode
Efficient electrolysis aquatic products hydrogen is realized from neutral aqueous solution or brine under 1.4V biass and produces oxygen, faradic efficiency reach 95% with
On, electro-catalysis production oxygen rate (TOF) reaches 0.8s-1.And this combination electrode shows good stability, by 10 hours
Electro-catalysis water oxygen, TON have reached 11000.But the catalytic current density of this combination electrode only has 220 μ A/cm2, and TOF values
Also it is very low.
2014, Sun Li was into seminar in catalyst [RuII(pda)(pic)3] framework counterpart on introduce 12 carbon
Alkoxy Long carbon chain synthesized the catalyst with strong-hydrophobicity, and utilize its hydrophobic performance and the multi-wall carbon nano-tube of carboxylated
Pipe (MWCNTsCOOH) is combined, using being prepared on the method mutual load to the carbon material substrate with satisfactory electrical conductivity of filtering
There is the combination electrode of electro-catalysis water oxidation susceptibility.It is demonstrated experimentally that this combination electrode shows good electro-catalysis water oxygen
Change performance, under the bias of 1.3V, initial catalyst current density is up to 4.5mA/cm2, TOF values are up to 12.4s-1, and can be with
Continuous firing 10 hours or more, faradic efficiency reaches 96%, TON up to more than 170000.But the catalysis of this combination electrode
Quickly, stability is not good enough for current density rate of decay, and after reaction in 1 hour, current density is reduced to 2mA/cm2, 5 hours
Afterwards, current density is down to 1mA/cm2Below.
Invention content
To solve problems of the prior art, the present invention provides a kind of ruthenium water oxidation catalysis based on elecrtonegativity ligand
Agent and preparation method thereof, ligand introduce two dodecyl carbochains on carbazole ring and synthesize new carbazole derivates, then with Ruization
Object is closed to carry out that complex Ru is obtained by the reaction.Complex Ru is applied in electro-catalysis water oxygen, with steady when improving its catalysis
It is qualitative.
To achieve the above object, the technical solution adopted by the present invention is：A kind of ruthenium water oxygen based on elecrtonegativity ligand is urged
Agent, the structure of catalyst are as follows：
A kind of preparation method of the ruthenium water oxidation catalyst based on elecrtonegativity ligand, includes the following steps：
Chemical compounds I and Ru (DMSO)4Cl2In Et3In N and anhydrous DMF, it is heated to 110 DEG C of reaction 12h；Then 4- is added
Picoline continues 90 DEG C and reacts 10 hours；Stop reaction, be cooled to room temperature, solvent is spin-dried for, obtain dark green powder production
Product；The chemical compounds I and Ru (DMSO)4Cl2Molar ratio be 1:1；Above step carries out under the conditions of anhydrous and oxygen-free.
The catalyst is applied in electro-catalysis water oxygen.
Beneficial effects of the present invention are：1st, the ligand of ruthenium water oxidation catalyst of the present invention has big conjugated system, effectively drops
The low overpotential of catalyst.
2nd, ruthenium water oxidation catalyst of the present invention introduces Long carbon chain in ligand, using the hydrophobicity of Long carbon chain, enhances and urges
The combination of agent and electrode.
3rd, ruthenium water oxygen method for preparing catalyst of the present invention is simple and practicable, and yield is higher, is easy to industrialize.
4th, ruthenium water oxidation catalyst of the present invention can show preferable photoelectrochemical in electro-catalysis water oxygen chemoattractant molecule device
Performance is learned, can be good at realizing that water oxygen puts oxygen, so as to provide effective half-reaction for water oxygen, to solve environmental problem
A kind of effective approach is provided with energy problem.
Description of the drawings
Fig. 1 is the 1H NMR spectras of novel carbazole derivative.
Fig. 2 is the crystal structure of complex Ru.
Fig. 3 is the structure of combination electrode Ru/MWCNTsCOOH/GC.
Fig. 4 is the scanning electron microscope (SEM) photograph of combination electrode Ru/MWCNTsCOOH/GC.
The EDX that Fig. 5 is electrode MWCNTsCOOH/GC and combination electrode Ru/MWCNTsCOOH/GC schemes.
Fig. 6 is the distribution diagram of element of combination electrode Ru/MWCNTsCOOH/GC.
Fig. 7 is the cyclic voltammetry scan test chart of combination electrode Ru/MWCNTsCOOH/GC.
Fig. 8 is combination electrode Ru/MWCNTsCOOH/GC potentiostatic depositions.
Fig. 9 is the current density test under the conditions of combination electrode Ru/MWCNTsCOOH/GC different potentials.
Figure 10 is the TOF values under the conditions of combination electrode Ru/MWCNTsCOOH/GC difference overpotentials.
Figure 11 is combination electrode Ru/MWCNTsCOOH/GC electrolysis tests for a long time.
Figure 12 is the faradic efficiency test of combination electrode Ru/MWCNTsCOOH/GC.
Figure 13 is the procedure chart of combination electrode Ru/MWCNTsCOOH/GC electro-catalysis water oxygens.
Specific embodiment
The present invention is further described with reference to embodiments：
The preparation of 1 carbazole derivates I of embodiment
Carbazole (5.02g, 30mmol) and 100mL CH are added in into 250mL two-mouth bottles2Cl2, it is stirred at room temperature down and is added portionwise
Aluminum trichloride (anhydrous) (9.33g, 70mmol) continues to be stirred to react 90 minutes, reaction is placed in ice-water bath and is cooled to 0 DEG C, delays
It is slow that dodecane acyl chlorides (15.30g, 70mmol) is added dropwise, reaction temperature is warmed to room temperature after being added dropwise, continues to be stirred to react 14 small
When.Reaction solution is poured into 200mL ice water, precipitation is collected by filtration, is eluted respectively with deionized water and methanol, collects thick production
Product are simultaneously recrystallized with methanol/acetone, are dried in vacuo to obtain white sterling 3,6- bis- (dodecanoyl) carbazole (11.20g, yield
70%).1H NMR(400MHz,CDCl3,):δ (ppm) 8.98 (br, 1H), 8.79 (s, 2H), 8.14 (d, J=8.8Hz, 2H),
7.49 (d, J=8.8Hz, 2H), 3.11 (t, J=7.2Hz, 4H), 1.90-1.80 (m, 4H), 1.45-1.20 (m, 32H), 0.88
(t, J=6.8Hz, 6H)13C NMR(400MHz,CDCl3):δ(ppm)200.12,142.85,130.14,127.05,
123.36,121.65,110.81,38.66,31.90,29.63,29.55,29.33,24.85,22.67,14.08.TOF-MS:
M/z=[M+H]+calcd:532.4155；found:532.4175.
Tetrahydrochysene lithium aluminium (3.04g, 80mmol), alchlor (5.33g, 40mmol) and the 120mL THF dried are added to
In 250mL round-bottomed flasks, 3,6- bis- (dodecanoyl) carbazole (10.60g, 20mmol) is added portionwise at 0 DEG C, reaction is stirred at room temperature
3 hours.Then the hydrochloric acid of 100mL ethyl acetate and 5mL 5% are slowly added dropwise into reaction solution, is filtered to remove insoluble matter, is spin-dried for
Filtrate obtains crude product, then with dichloromethane/n-hexane=2:1(V:V silica gel post separation) is carried out for eluant, eluent, obtains white
Solid product (7.16g, 71%).1H NMR(400MHz,CDCl3):δ(ppm)7.85(s,2H),7.82(br,1H),7.29
(d, J=8.4Hz, 2H), 7.21 (d, J=8.4Hz, 2H), 2.76 (t, J=7.6Hz, 4H), 1.75-1.60 (m, 4H), 1.45-
1.20 (m, 36H), 0.88 (t, J=6.8Hz, 6H)13C NMR(400MHz,CDCl3):δ(ppm)138.19,133.81,
126.38,123.37,119.51,110.16,36.05,32.37,31.92,29.69,29.64,29.61,29.39,29.36,
22.69,14.13.TOF-MS:M/z=[M+H]+calcd:504.4569；found:504.4593.
3,6- bis- (dodecyl) carbazole (2.50g, 5mmol) and 60mL glacial acetic acid are added in 100mL round-bottomed flasks,
It is stirred at room temperature under the conditions of being protected from light, bromine (0.60mL, 12mmol) is added dropwise into reaction solution, continue room temperature reaction 1 hour.Reaction knot
Shu Hou adds in the thio saturated aqueous solution of sodium 50mL of saturation sulfuric acid, is extracted with ethyl acetate (3 × 100mL), collects organic
Phase adds in anhydrous magnesium sulfate and is dried, filters, be spin-dried for filtrate and obtain yellow solid product 1, bis- bromo- 3,6-, bis- (dodecanes of 8-
Base) carbazole (3.20g, 98%).1H NMR(400MHz,CDCl3):δ(ppm)8.08(br,1H),7.89(s,2H),7.60(d,J
=8.1Hz, 2H), 2.72 (t, J=7.4Hz, 4H), 1.78-1.62 (m, 4H), 1.41-1.10 (m, 36H), 0.86 (t, J=
6.5Hz,6H).TOF-MS:M/z=[M+H]+calcd:660.2780；found:660.2798.
Bis- bromo- 3,6- bis- (dodecyl) carbazoles (2.64g, 4mmol) of 1,8-, cuprous cyanide (0.92g, 10mmol) and
40mL N-Methyl pyrrolidones are added in 100mL two mouth flasks, and heating reflux reaction is overnight.Stop reaction being cooled to room temperature,
Saturation liquor ferri trichloridi (80mL) and ethyl acetate (50mL) are added in into reaction solution, continues to stir half an hour, crosses and filter out
Insoluble matter is removed, filtrate is extracted with ethyl acetate (3 × 100mL), merges organic phase, is washed with sodium chloride solution (2 × 50mL), is received
Collect organic phase and add in anhydrous magnesium sulfate and be dried, filter, be spin-dried for filtrate and obtain crude product, then recrystallized with ethyl acetate
Obtain two (dodecyl) carbazoles (1.77g, 80%) of solid product 1,8- dicyanos -3,6-.1H NMR(400MHz,CDCl3):δ
(ppm) 9.87 (s, 1H), 8.21 (d, J=1.5Hz, 2H), 7.85 (d, J=1.6Hz, 2H), 2.74 (t, J=6.8Hz, 4H),
1.75-1.60 (m, 4H), 1.45-1.10 (m, 36H), 0.83 (t, J=5.5Hz, 6H) .TOF-MS:M/z=[M+H]+calcd:
554.4474；found:554.4492.
1,8- dicyanos -3,6- two (dodecyl) carbazole (1.66g, 3mmol) and NaOH (1.20g, 30mmol) are added
In the 100mL two-mouth bottles for entering to fill 20mL deionized waters, heating reflux reaction is overnight, until reactant all dissolves.Stop anti-
Should, it is cooled to room temperature, the pH value of reaction solution is adjusted to 1 with concentrated hydrochloric acid, discovery has a large amount of precipitation generations, and decompression is filtered, washed, receives
Collect filter cake, obtain the product in a vacuum and drying environment 1,8- dicarboxyls -3,6- bis- (dodecyl) carbazole (1.70g, 96%).1H NMR
(500MHz,d6-DMSO):δ (ppm) 10.94 (s, 0.5H), 8.30 (s, 1H), 7.86 (s, 1H), 2.76 (t, J=7.2Hz,
2H), 1.78-1.60 (m, 2H), 1.42-1.08 (m, 18H), 0.81 (t, J=5.4Hz, 3H) .TOF-MS:M/z=[M-H]-
calcd:590.4209；found:590.4237.
Embodiment 2 is using carbazole dicarboxylic acid derivatives as the preparation of the metal complex Ru of skeleton
Chemical compounds I and Ru (DMSO)4Cl2In Et3In N and anhydrous DMF, it is heated to 110 DEG C of reaction 12h.Then 4- is added
Picoline continues 90 DEG C and reacts 10 hours.Stop reaction, be cooled to room temperature, solvent is spin-dried for, obtain dark green powder production
Product.Chemical compounds I and Ru (DMSO)4Cl2Molar ratio be 1:Isosorbide-5-Nitrae-picoline is excessive.Above step is in anhydrous and oxygen-free
Under the conditions of carry out.
Finally, with CH2Cl2/CH3OH=100:1(V:V silica gel post separation) is carried out for eluant, eluent, obtains greenish solid product
(yield 45%).TOF-MS:M/z=[M+H]+calcd:970.4910；Found, 970.4941.m/z=[M+Na]+calcd:
992.4730；found:992.4754.Elem.anal:calcd.for C56H75N4O4Ru (%):C 69.32,H 7.74,N
5.78；found,C 69.23,H 7.72,N 5.88.
The crystal culture of 3 metal complex Ru of embodiment and parsing
The crystal cultural method of complex：It is slowly added to 0.1mL's into methanol solutions of the 5mL dissolved with complex (15mg)
Deionized water is sealed, and is stored at room temperature five days, by the phase counterdiffusion whole system supersaturation of first alcohol and water, is precipitated
It is suitble to the green crystal of monocrystalline test.
The test of X-ray single crystal diffraction has been carried out to the structure of complex, has obtained its X-ray single crystal diffraction data.Tool
Body examination test instrument is shown in that chapter 2 2.2.3 is saved with method.The crystallographic parameter and test parameter of complex are shown in Table 1.
The crystal test data and relevant parameter of 1 complex Ru of table
It is tested by X-ray single crystal diffraction, obtains the Accuracy Space structure of complex Ru (see Fig. 2).Complex Ru is main
Bond distance and bond angle be listed in Table 2 below, No. CCDC of crystal is CCDC -1499670.
The main bond distance of 2 complex Ru of table and bond angle data
It is parsed by the crystal data to complex Ru, identical (without Long carbon chain) with framework counterpart carbazole is known
Compound compares, and the main bond distance of complex Ru and bond angle are about the same with it.This shows introduced on framework counterpart carbazole two
A Long carbon chain does not have an impact the coordination of central metal Ru.Meanwhile two Long carbon chains to freely swing cause complex
Ru has extremely strong hydrophobicity, can act on combination well between carbon nanotube.
The preparation of 4 combination electrode Ru/MWCNTsCOOH/GC of embodiment
(1) preparation of electrode MWCNTsCOOH/GC
The pretreatment of glassy carbon electrode：It is polished 5 minutes, is cleaned with deionized water, Ran Houchao for 3 μm of alumina powders with grain size
Sound cleans 10 minutes, is dried with lens paper spare.
The preparation of MWCNTsCOOH dispersion liquids：5mg MWCNTsCOOH are placed in 5mL THF, 20min is ultrasonically treated, obtains
To the THF dispersion liquids of MWCNTsCOOH.
60 μ L MWCNTsCOOH dispersant liquid drops is taken to be coated onto glassy carbon electrode surface, control area 1cm with liquid-transfering gun2, treat
THF volatilizations are complete, repeat this operation twice.MWCNTsCOOH/GC electrodes are obtained, is put into baking oven and is dried for standby for 70 DEG C.
(2) preparation of combination electrode Ru/MWCNTsCOOH/GC
The MWCNTsCOOH/GC electrodes prepared are immersed in the methanol solution of the complex Ru of 1.0mM overnight, taken out
The catalyst solution of electrode surface remaining, N are rinsed out with 0.1mL methanol later2It is compound that drying obtains Ru/MWCNTsCOOH/GC
Electrode (see Fig. 3).
For the relatively common carbon nanotube of the carbon nanotube of carboxylated, between hydrone there is certain hydrogen bond to make
With the activity of the electrochemical catalysis water oxygen of electrode can be improved.Therefore, the application uses the carboxylic of Aladdin Reagent Company production
Carrier material of the base multi-walled carbon nano-tube as supporting molecular catalyst, while select the vitreous carbon with excellent conductive performance
Functionalized multi-wall carbonnanotubes are loaded into glass carbon surface as base material, and using simple drop-coating, are then utilized
The method of immersion is by catalyst loading to carbon nanotube, and so as to prepare combination electrode, this preparation method is simple to operation, and
With good repeatability.In addition, combination electrode prepared by this method have the advantages that it is reusable, in test completion
Afterwards, sanding and polishing is carried out to electrode, again with methanol solution can be used for preparing combination electrode again after being ultrasonically treated, this is for after
Commercial applications have great importance.
From the scanning electron microscope (SEM) photograph (Fig. 4) of combination electrode as can be seen that the carbon nanotube on glassy carbon electrode surface is interweaved
Overlapping shows unordered porous structure, therefore with very big specific surface area, and the load for molecular catalyst provides guarantor
Barrier.In addition, the energy dispersion X-ray light by comparison electrode MWCNTsCOOH/GC and combination electrode Ru/MWCNTsCOOH/GC
The test result (Fig. 5) of (EDX) is composed, can be clearly observable on Ru/MWCNTsCOOH/GC combination electrodes has metal Ru, it was demonstrated that
Molecular catalyst has been loaded on electrode really.While sem test, the essential element of electrode surface is distributed into
It has gone analysis (Fig. 6), test analysis has been carried out in the one piece of region randomly selected, the results show that the C element and Ru of electrode surface
Elemental redistribution is all visibly homogeneous, this shows that molecular catalyst on combination electrode surface is equally distributed.
The electrochemical test method and condition of 5 combination electrode Ru/MWCNTsCOOH/GC of embodiment
Select Shanghai Hua Chen companies CHI 630E types electrochemical workstations to Ru/MWCNTsCOOH/GC combination electrodes into
Row cyclic voltammetric and potentiostatic deposition test, in pH 7.0 phosphate buffer solution of the ionic strength (IS) for 0.1M, with 1cm2
Platinum guaze do to electrode, with Ag/AgCl (3.5M saturation KCl solution) for reference electrode, all current potentials pass through Ru (bpy)3 2+
(RuII/RuIII=1.26V vs.NHE) carry out reference corrected.All potentiostatic deposition tests do not carry out iR drop voltage compensations.
The application of the electro-catalysis water oxygen of 6 combination electrode Ru/MWCNTsCOOH/GC of embodiment
It is surveyed by carrying out cyclic voltammetry scan (sweep speed 100mV/s) to combination electrode Ru6/MWCNTsCOOH/GC
It tries (Fig. 7), it is observed that combination electrode Ru/MWCNTsCOOH/GC has good electrochemical catalysis water oxidation activity,
E1/2For that can be clearly observed a pair of of redox peaks at 0.59V, this corresponding oxidation-reduction process is complex Ru
RuIII/RuIVProcess.By to RuIII/RuIVRedox peak to peak current integrates to obtain electricity as (2.9 ± 0.3) × 10-5C, into
And by Faraday's law formula Γ=Q/ (nsF), (n is electron transfer number, equal to 1；S is the work area of electrode, is equal to
1cm2；F is Faraday constant, equal to 9.65 × 104C/mol), the adsorbance that can calculate catalyst on this combination electrode is
(3±0.3)×10-10mol/cm2.Cyclic voltammetry also shows the startup current potential of this combination electrode electrochemical catalysis water oxygen
For 1.2V, overpotential is only 380mV.MWCNTsCOOH/GC electrodes and GC electrodes without modified catalyst is in cyclic voltammetric
Any redox peaks are then not observed in scanning range, this illustrates work of this two electrode almost without electro-catalysis water oxygen
Property.
Further to investigate the electro-catalysis water oxidation activity of combination electrode Ru6/MWCNTsCOOH/GC, with the phosphorus of pH 7.0
Acid rushes solution as electrolyte, and the work area of coordination electrode is 1cm2, potentiostatic deposition has been carried out under the applying bias of 1.4V
Experiment, the results are shown in Figure 8.During electrolysis, a large amount of bubble can be clearly observed constantly from Pt net cathodes
With being released on Ru/MWCNTsCOOH/GC anodes, respectively hydrogen and oxygen are determined through gas chromatographic detection.By the electricity of 2 hours
Solution experiment, current density maintain 1.25mA/cm2Left and right is undamped, shows the combination electrode for electrochemical catalysis water oxygen
Hydrogen production reaction has good stability.
(1) Tafel and the TOF test of combination electrode Ru/MWCNTsCOOH/GC
The electro-catalysis water oxygenization for carrying out control time under different biass to combination electrode Ru6/MWCNTsCOOH/GC is surveyed
Examination, obtains the catalytic current density (Fig. 9) under the conditions of different overpotentials.Then catalytic current density is taken the logarithm as ordinate
It maps with overpotential as abscissa, the Tafel curves (Figure 10) of combination electrode can be obtained.
It can be seen from fig. 10 that in the range of the overpotential of 380mV to 780mV, the Tafel of combination electrode is straight in one
Line.By formula TOF=Q/ (4tF Γ) (Q be electrolytic process in by electricity, unit C；F is Faraday constant, is equal to
9.65×104C/mol；Times of the t for cell reaction, unit s；Adsorbances of the Γ for catalyst, unit mol) it can count
Calculate TOF value of the combination electrode under different overpotentials.As overpotential from 380mV increases to 780mV, the TOF values of electrode
Accordingly from 2.2s-1Increase to 31.5s-1, this illustrates that this electrode has very high electro-catalysis water oxidation activity.
(2) the electro-catalysis water oxygen stability test of combination electrode Ru/MWCNTsCOOH/GC
Stability for the electro-catalysis water oxidation reaction for further assessing combination electrode Ru6/MWCNTsCOOH/GC, this hair
It is bright that combination electrode has been carried out to be electrolysed test for a long time.It can be seen that electrode after being electrolysed 10 hours from the test result of Figure 11
Catalytic current density still has 1mA/cm2, this result proves that combination electrode Ru6/MWCNTsCOOH/GC is urged showing very high electricity
Also there is good stability while changing water oxidation activity.The intermediate that such catalyst generates in catalytic water oxidation process
For electroneutral, that is to say, that complex Ru is always electroneutral in entire catalytic water oxidation reaction process, this guarantees with
It closes object Ru to be not easy to come off from electrode surface in electrolytic process, this conclusion is consistent with the result of electrolysis test.
The faradic efficiency test of 7 combination electrode Ru/MWCNTsCOOH/GC of embodiment
Using Tianjin Ida company can closed electrolytic pond the faraday of combination electrode Ru6/MWCNTsCOOH/GC is imitated
Rate is tested.First, a certain amount of 7.0 buffer solutions of pH will be added in electrolytic cell as electrolyte, then by combination electrode,
Gauze platinum electrode is fixed with Ag/AgCl electrodes, is sealed electrolytic cell with polytetrafluoro adhesive tape, and argon gas progress is then blasted into electrolytic cell
Deoxygenation, after the completion of vapor detection deoxygenation, at regular intervals often, using the method for hand sampling by gas-chromatography to electrolytic cell
The hydrogen of interior generation is detected and quantitative with oxygen, finally by faradic efficiency value is calculated.Test result is shown in Figure 12.
Faradic efficiency refer in electro-catalysis water oxidation reaction process for produce in the quantity of electric charge and circuit of oxygen by it is total
The ratio between quantity of electric charge, for water oxidation reaction, often generating an oxygen molecule needs to consume four charges, therefore faraday is imitated
Rate can pass through formula η=4nO2/Q (nO2For the amount of oxygen generated in electrolytic process, unit mol；Q is to lead in electrolytic process
The total charge dosage crossed, unit mol).Electrolysis test for a long time is carried out in closed electrolytic cell, under 1.4V voltages, is passed through simultaneously
Gas-chromatography quantifies the oxygen generated in electrolytic process, and after being electrolysed 10 hours, the amount of oxygen for detecting generation is 107.8
μm ol, be converted into electricity in 41.6C, with electrolytic process by total electricity 43.1C coincide, be computed learning combination electrode
The faradic efficiency of electro-catalysis water oxidation reaction is up to 96%, TON and reaches 360000.At the same time, pass through vapor detection to life
Into amounts of hydrogen for 217.4 μm of ol, the ratio with oxygen is 2:1.
The present invention is not limited to ruthenium water oxidation catalyst, Preparation method and use recorded in above-described embodiment, preparation side
The change of method is within protection scope of the present invention.
Electro-catalysis water oxygen chemoattractant molecule device is a kind of purposes of ruthenium water oxidation catalyst of the present invention, it is impossible to assert ruthenium of the present invention
Water oxidation catalyst is only used for water oxidation catalyst, for those of ordinary skill in the art to which the present invention belongs, in base
Under the considerations of ruthenium water oxidation catalyst of the present invention is used for the same mechanism of water oxidation catalyst, it can also make and several simply push away
Reason, obtains the other application purposes of the compound of the present invention, should all be considered as belonging to protection scope of the present invention.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Pipe is described in detail the present invention with reference to foregoing embodiments, it will be understood by those of ordinary skill in the art that：Its according to
Can so modify to the technical solution recorded in foregoing embodiments either to which part or all technical features into
Row equivalent replacement；And these modifications or replacement, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (3)
1. a kind of ruthenium water oxidation catalyst based on elecrtonegativity ligand, which is characterized in that the structure of the catalyst is as follows：
2. a kind of preparation method of ruthenium water oxidation catalyst based on elecrtonegativity ligand according to claim 1, feature
It is, includes the following steps：
Chemical compounds I and Ru (DMSO)4Cl2In Et3In N and anhydrous DMF, it is heated to 110 DEG C of reaction 12h；Then 4- methyl is added
Pyridine continues 90 DEG C and reacts 10 hours；Stop reaction, be cooled to room temperature, solvent is spin-dried for, obtain dark green powder product；Institute
State chemical compounds I and Ru (DMSO)4Cl2Molar ratio be 1:1；Above step carries out under the conditions of anhydrous and oxygen-free.
3. a kind of application of ruthenium water oxidation catalyst based on elecrtonegativity ligand according to claim 1, it is characterised in that：
The catalyst is applied in electro-catalysis water oxygen.
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