A kind of Pt-WC/ Graphene composite electrocatalyst and preparation method thereof
(1) technical field
The present invention relates to a kind of composite electrocatalyst and preparation method thereof, particularly a kind of Pt-WC/ Graphene composite electrocatalyst and preparation method thereof.
(2) background technology
In eelctro-catalyst, catalyst carrier has significant impact to the performance of catalyst performance.All kinds of conductive carbon materials; Their forms are different, and pattern is different, is used as electro-catalyst carrier like active carbon, multi-walled carbon nano-tubes, SWCN etc.; Active carbon wherein is widely used in fuel-cell catalyst carrier, and CNT has also obtained extensive studies and development as carrier.But with above-mentioned material with carbon element is that the catalyst of preparing carriers has mostly used a large amount of noble metal platinums, causes the catalyst cost too high, and their catalytic activity is not very high, the easy reunion, causes stability also to have certain problem.
In order to overcome the problem that above-mentioned catalyst exists, research and develop a kind of new eelctro-catalyst, the cost of catalyst is significantly reduced, and the utilization rate of noble metal platinum is improved, its electrocatalysis characteristic is strengthened.Graphene (Graphene) is the bi-dimensional cellular shape crystal of the monatomic thickness that is made up of carbon atom, and carbon atom arrangement is the same with the monoatomic layer of graphite, and it is considered to the basic structural unit of fullerene, CNT and graphite.Layer structure material with carbon element after we reduce graphite oxide is referred to as grapheme material (RGO); It has similarly a series of good peculiar character of single-layer graphene, and specific area is higher, and more metal load byte can be provided; Simultaneously; Graphene shows very strong quantum effect and outstanding chemical stability, has superior machinery and Electronic Performance, can be used as an ideal template supported catalyst.
Tungsten carbide (WC) is a kind of crystal with hexagonal structure, has characteristics such as high rigidity, high-wearing feature, high-melting-point, is widely used in the fields such as microbit, precision die and medical device of cutting element, electronics industry as carbide alloy.On the other hand, tungsten carbide has good corrosion resistance and non-oxidizability, and the surface electronic structure of tungsten carbide and Pt are similar promptly has an eka-platinium performance, in some chemical reactions, has good catalytic activity as catalyst, does not receive the CO and the 1O of any concentration
-6The H of the order of magnitude
2S poisons, and has good stable property and anti-poisoning performance, and cheap, is a kind of catalyst that has the development and application potentiality.Tungsten carbide also has good electrical conductivity simultaneously, is applied to fields such as electrochemical catalysis and fuel cell as electrode.Existing research shows; Also have certain distance though the catalytic activity of tungsten carbide is compared with pure platinum, following tungsten carbide substitutes have a high potential (Daniel V.Esposito, the Jingguang G.Chen of platinum; Monolayer platinum supported on tungsten carbides as low-cost electrocatalysts:opportunities and limitations; Energy environ.sci., 2011, Advance Article; Erich C.Weigert; Alan L.Stottlemyer, Michael B.Zellner, and Jingguang G.Chen; Tungsten Monocarbide as Potential Replacement of Platinum for Methanol Electrooxidation; 2007,111,14617-14620).Therefore; With the Graphene is catalyst carrier; With the tungsten carbide nanoparticulate dispersed on Graphene lamella structure, the WC/RGO of preparation again in the load nanometer Pt particle synthesize the Pt-WC/RGO composite catalyst and should have good electrocatalysis characteristic, especially to anodic oxidation of methanol.
(3) summary of the invention
The object of the invention provides a kind of Pt-WC/ Graphene composite electrocatalyst and preparation method thereof; This catalyst is carrier with the Graphene; With tungsten carbide and small amounts of platinum is dual-active property component, and the method that combines through dipping reduction and carbonization and heating using microwave liquid phase coreduction prepares step by step, has realized the homogeneous and controllable load of active particle on the RGO surface; Show that through Electrochemical Detection this catalyst can significantly improve the catalytic performance to methanol electro-oxidizing.
The technical scheme that the present invention adopts is:
A kind of Pt-WC/ Graphene composite electrocatalyst, said catalyst are carrier with the Graphene, are active component with tungsten carbide (WC) and platinum (Pt), and the load capacity of tungsten carbide is 10~50%, and the load capacity of platinum is 5~10%.
Further, said catalyst is carrier with the Graphene, is active component with tungsten carbide and platinum, and the load capacity of tungsten carbide is preferably 10~30%, and the load capacity of platinum is preferably 5~8%.
The present invention provides a kind of method of the Pt-WC/ of preparation Graphene composite electrocatalyst, and said method is: graphite oxide impregnated in the ammonium metatungstate aqueous solution, obtain mixed liquor; Fully the dipping back is dry, obtains ammonium metatungstate/graphite oxide powder, is reduction and carbonization gas again with CO; Ammonium metatungstate in 400~900 ℃ of procedural heating reduction carbonization ammonium metatungstate/graphite oxide powder; Get tungsten carbide/graphite oxide powder, in tungsten carbide/graphite oxide powder, add ethylene glycol again, add chloroplatinic acid aqueous solution after the ultrasonic dispersion; Heating using microwave to 100~120 ℃; Reaction 15~25min, reactant liquor obtains Pt-WC/ Graphene composite electrocatalyst through filtration, deionized water washing, oven dry; The theoretical negative carrying capacity of tungsten carbide counts 10~50% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder; The theoretical negative carrying capacity of platinum counts 5~10% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder; Said ethylene glycol volumetric usage is counted 0.29~0.77ml/mg with tungsten carbide/graphite oxide powder quality; The volumetric usage of said chloroplatinic acid aqueous solution is counted 0.02~0.12ml/mg with tungsten carbide/graphite oxide powder quality, and the molar concentration of said chloroplatinic acid aqueous solution is 0.005mol/L, and the feeding amount of said CO is 100ml/min; The content of graphite oxide is 10.6~19.7mg/ml mixed liquor in the said mixed liquor; Preferred 10.64~19.74mg/ml mixed liquor, the content of said ammonium metatungstate are 1.5~10.4mg/ml mixed liquor, preferred 1.52~10.44mg/ml mixed liquor.
Further, said Pt-WC/ Graphene composite electrocatalyst preparation method is following:
1) preparation of graphite oxide (GO): graphite powder and concentrated sulfuric acid solution are mixed, behind the stirring 30min, slowly add KMnO in the ice bath
4, 5~15 ℃ of reaction 2h stir 40min at 30~40 ℃ again; Slowly add deionized water A; 95~100 ℃ of reaction 1h slowly add deionized water B and mass fraction and are 30% hydrogen peroxide solution again, naturally cool to that the adding mass concentration is 18% aqueous hydrochloric acid solution after the room temperature; Above-mentioned reactant liquor is centrifugal, precipitate with deionized water is washed, drying, obtains the graphite oxide powder; Said graphite powder and KMnO
4Mass ratio be 1: 3; Said concentrated sulfuric acid volumetric usage is the 23ml/g graphite powder; The volumetric usage of said hydrogen peroxide solution is the 30ml/g graphite powder; The volumetric usage of said aqueous hydrochloric acid solution is the 14ml/g graphite powder, and the volumetric usage of said deionized water A is the 50ml/g graphite powder, and the volumetric usage of said deionized water B is the 20ml/g graphite powder;
2) be dispersed in the ammonium metatungstate aqueous solution graphite oxide is ultrasonic, fully mix, obtain mixed liquor, 85 ℃ are stirred the evaporate to dryness mixed liquors, obtain ammonium metatungstate/graphite oxide powder; The content of graphite oxide is 10.6~19.7mg/ml mixed liquor in the said mixed liquor, and the content of said ammonium metatungstate is 1.5~10.4mg/ml mixed liquor, and the concentration of said ammonium metatungstate aqueous solution is generally 1.6~11.9mg/ml; The mass ratio of graphite oxide and ammonium metatungstate is 1.9~7.3 in the said mixed liquor;
3) ammonium metatungstate (AMT)/graphite oxide powder being put into the high-temperature tubular carbide furnace, is reduction and carbonization gas with CO, adopts temperature-programmed mode reduction and carbonization ammonium metatungstate, gets tungsten carbide (WC)/graphite oxide powder; The theoretical negative carrying capacity of said tungsten carbide counts 10~30% with the graphite oxide quality; The feeding amount of CO is 100ml/min;
4) in tungsten carbide/graphite oxide powder, add ethylene glycol (EG); The ultrasonic dispersion of 180W back adds chloroplatinic acid aqueous solution; 180W is ultrasonic again is uniformly dispersed, and regulates between the pH value 9~10 heating using microwave to 100~120 ℃ reaction 15~25min; Reactant liquor cooling after filter, deionized water washing, oven dry, obtain Pt-WC/ Graphene composite electrocatalyst; Said ethylene glycol volumetric usage is counted the volumetric usage of 0.29~0.77ml/mg, said chloroplatinic acid aqueous solution and is counted 0.02~0.12ml/mg with tungsten carbide/graphite oxide powder quality with tungsten carbide/graphite oxide powder quality, the molar concentration of said chloroplatinic acid aqueous solution is 0.005mol/L; The theoretical negative carrying capacity of said platinum counts 5~8% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder.
Said temperature-programmed mode reduction and carbonization ammonium metatungstate carries out as follows: earlier logical N2 continues 30min and removes the tubular type furnace air; Adopting CO is reduction and carbonization gas; Vacuum tube furnace 30min is set is warming up to 400 ℃ of maintenance 1h; 30min is warming up to 900 ℃ of maintenance 4h then, and the reduction and carbonization ammonium metatungstate gets the WC/GO powder.
The volumetric usage of said chloroplatinic acid aqueous solution is preferably 0.049~0.062ml/mg in tungsten carbide/graphite oxide quality.
The preparation method of graphite oxide according to the invention is with reference to Fu Ling, Liu Hongbo, and Zou Yanhong, Li Bo, the Hummers legal system influences the technological factor research [J] of degree of oxidation when being equipped with graphite oxide, and charcoal is plain, and 2005,4 (124): 10-14).
Deionized water A according to the invention and deionized water B are deionized water, name for ease of the statement of distinguishing different step.
The present invention is at first through being dispersed in the graphite oxide powder in the ammonium metatungstate aqueous solution, and the dipping evaporating water obtains AMT/GO, and reduction and carbonization obtains tungsten carbide/graphite oxide (WC/GO) in vacuum tube furnace again, and then is preparing carriers Pt-WC/RGO with it.Done following advantage like this:
(1) ammonium metatungstate can well be water-soluble; Water is cooked solvent and has also been avoided the introducing of impurity (saved and removed impurity institute trouble caused), and graphite oxide has abundant hydrophily oxygen-containing functional group, like hydroxyl, carbonyl, carboxyl and epoxy radicals etc.; So the aqueous solution of ammonium metatungstate can be easy to enter into the interlayer of graphite oxide; And form the load site with these functional groups, for the nucleation of back WC provides advantage, also played good peptizaiton simultaneously;
(2) carbonisation of back is to adopt temperature programming control, also goes up the reunion that can avoid WC particle to a certain degree;
(3) the synthetic Pt-WC/RGO of substep can effectively avoid platinum grain that self reunion takes place, and helps the dispersion and the performance catalytic performance of particle, has significantly improved the utilization rate of platinum.
Compared with prior art; Beneficial effect of the present invention is mainly reflected in: course of reaction of the present invention and active particle controlled amount; Used WC is cheap and possess some row excellent chemical character; As can significantly reducing the eelctro-catalyst cost for platinum catalyst, improve its catalytic performance simultaneously, be expected to quicken the commercial paces of fuel cell.
(4) description of drawings
Fig. 1 is Pt-WC/ Graphene composite electrocatalyst preparation flow figure
Fig. 2 is the sem photograph (SEM) of graphite oxide
Fig. 3 is the transmission electron microscope picture (TEM) of graphite oxide
Fig. 4 is the TEM figure of tungsten carbide/graphite oxide (WC/GO)
Fig. 5 is the TEM figure of Pt-WC/ Graphene composite electrocatalyst
Fig. 6 is the EDS figure of Pt-WC/ Graphene composite electrocatalyst
(5) specific embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
The load capacity of said WC and Pt is that benchmark calculates with the quality of GO all.
The sem photograph of graphite oxide (SEM) adopts Hitachi S4700 type field emission scanning electron microscope (Japanese Hitachi company) test.
The transmission electron microscope picture of graphite oxide (TEM) adopts TecnaiG2 F30 S-Twin type high resolution transmission electron microscopy (Dutch Philip-FEI company) test.
The EDS figure of Pt-WC/ Graphene composite electrocatalyst adopts X-ray energy spectrometer (Therrmo NORAN VANTAGE EIS company) test.
Embodiment 1
(1) preparation of graphite oxide (GO): with the dense H of 1g graphite powder (spectroscopic pure, traditional Chinese medicines group) and 23mL 98%
2SO
4Solution mixes, and behind the mechanical agitation 30min, slowly adds 3g KMnO in the ice bath
4, keep temperature to continue to stir 2h for 10 ± 5 ℃.Then it is transferred in the water bath with thermostatic control, keeps temperature to continue to stir 40min for 35 ± 5 ℃, finish the back and slowly add the 50mL deionized water; 95~100 ℃ of temperature maintenance, reaction 1h slowly adds the 20mL deionized water then; Slowly add 30mL 30% hydrogen peroxide solution again; Add 14mL 18% hydrochloric acid solution after naturally cooling to room temperature,, promptly get graphite oxide powder 1.5g after precipitate with deionized water washing, the drying the centrifugal 10min of above-mentioned reactant liquor 3000rpm; Graphite oxide sem photograph (SEM) and transmission electron microscope picture (TEM) are seen Fig. 2 and shown in Figure 3;
(2) the 32.3mg ammonium metatungstate is dissolved in the 20mL deionized water, adds 236.5mg graphite oxide (GO) powder, ultrasonic being uniformly dispersed; Obtain the 21.3mL mixed liquor; This mixture is transferred in the oil bath pan, 85 ℃ of reaction temperatures are set, stir while flooding; Until the whole moisture of evaporate to dryness, get AMT/GO powder 268mg;
(3) with the AMT/GO powder transfer of drying to quartz boat, be put in vacuum tube furnace (OTF-1200X, brilliant Materials Technology Ltd. of Hefei section) lining; Adopt CO as carbonizing reduction gas; Gas flow is 100ml/min, vacuum tube furnace 30min is set is warming up to 400 ℃ and keep 1h, and 30min is warming up to 900 ℃ and keeps 4h again; AMT all is reduced carbonization and gets the WC/GO powder with this understanding, and the theoretical negative carrying capacity of said tungsten carbide counts 10% with the graphite oxide quality;
(4) after the above-mentioned WC/GO powder cooling; WC/GO powder (GO Theoretical Mass 54.9mg) adds 20mL ethylene glycol in the microwave reaction pipe after getting the 61.0mg carbonization; Add 3.0mL 0.005mol/L chloroplatinic acid aqueous solution behind the ultrasonic 1h of 180W, the ultrasonic dispersion of 180W 1h again, the pH value of conditioned reaction system is 9~10 then; This system is transferred in the microwave reactor, reacted 15min under 100 ℃ of conditions.After being cooled to room temperature; Through filtration, deionized water washing, oven dry; Obtain Pt-WC/ Graphene composite electrocatalyst (the theoretical negative carrying capacity of WC counts 10% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder, and the theoretical negative carrying capacity of Pt counts 5% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder); Tungsten carbide/graphite oxide (WC/GO) transmission electron microscope picture is seen Fig. 4; The TEM figure of Pt-WC/ Graphene composite electrocatalyst is as shown in Figure 5; The X-ray energy spectrum (EDS) of Pt-WC/ Graphene composite electrocatalyst is seen shown in Figure 6;
(5) preparation of working electrode: 5% Nafion solution and the 80 μ l ethanol of 5mg Pt-WC/ Graphene composite electrocatalyst and 40 μ l are mixed under the ultrasonic wave effect; Be coated on the glassy carbon electrode with the liquid-transfering gun mixed pulp drop that takes a morsel, dry the back naturally as measuring working electrode; And with commercial platinum carbon (mass fraction of Pt is 20%, Johnson Matthey) catalyst as contrast;
(6) the test job electrode and with commercial platinum C catalyst electrocatalysis characteristic relatively: measure the three-electrode system of employing standard, the large tracts of land platinized platinum is to electrode, and saturated calomel electrode (SCE) is a reference electrode, and electrolyte is 0.5mol/L H
2SO
4+ 1.0mol/L CH
3OH solution.Estimate eelctro-catalyst to the methanol oxidation electro catalytic activity with cyclic voltammetry (CV), sweep speed is 50mv/s.Record above-mentioned two kinds of eelctro-catalysts the peak current of methanol electro-oxidizing is respectively 539.0mA/mgPt and 311.7mA/mgPt, presentation of results Pt-WC/ Graphene eelctro-catalyst has higher methanol oxidation catalytic performance than commercial platinum C catalyst.
Embodiment 2:
(1) preparation method of graphite oxide is with reference to the step (1) of embodiment 1;
(2) the 238mg ammonium metatungstate is dissolved in the 20mL deionized water, adds 450mg graphite oxide (GO) powder, ultrasonic being uniformly dispersed; Obtain the 22.8mL mixed liquor; This mixed liquor is transferred in the oil bath pan, 85 ℃ of reaction temperatures are set, stir while flooding; Until the whole moisture of evaporate to dryness, get AMT/GO powder 672mg;
(3) preparation method of WC/GO is with reference to the step (3) of embodiment 1;
(4) after the cooling; WC/GO powder (Theoretical Mass of GO is 18.2mg) adds 20mL ethylene glycol in the microwave reaction pipe after getting the 26.0mg carbonization; Add the 1.6mL0.005mol/L chloroplatinic acid aqueous solution behind the ultrasonic 1h of 180W, the ultrasonic dispersion of 180W 1h again, the pH value of conditioned reaction system is 9~10 then; This system is transferred in the microwave reactor, reacted 20min under 120 ℃ of conditions.After being cooled to room temperature; Through filtration, deionized water washing, oven dry; Obtain Pt-WC/ Graphene composite electrocatalyst (the theoretical negative carrying capacity of WC counts 30% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder, and the theoretical negative carrying capacity of Pt counts 8% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder);
(5) method of the preparation of working electrode is with reference to the step (5) of embodiment 1;
(6) the test job electrode and with the step (6) of commercial platinum C catalyst electrocatalysis characteristic comparative approach with reference to embodiment 1; Recording Pt-WC/ Graphene composite electrocatalyst is 848.5mA/mgPt to the peak current of methanol electro-oxidizing; Far above the 311.7mA/mgPt of commercial platinum C catalyst, presentation of results Pt-WC/ Graphene eelctro-catalyst has higher methanol oxidation catalytic performance than commercial platinum C catalyst.
Embodiment 3:
(1) preparation method of graphite oxide is with reference to the step (1) of embodiment 1;
(2) the 69.0mg ammonium metatungstate is dissolved in the 20mL deionized water, adds 224.5mg graphite oxide powder, ultrasonic being uniformly dispersed; Obtain mixture 21.1ml, this mixed liquor is transferred in the oil bath pan, 85 ℃ of temperature are set; Stir while flooding,, get AMT/GO powder 291mg until the whole moisture of evaporate to dryness;
(3) preparation method of WC/GO is with reference to the step (3) of embodiment 1;
(4) after the cooling; WC/GO powder (Theoretical Mass of GO is 53.6mg) adds 20mL ethylene glycol in the microwave reaction pipe after getting the 67.0mg carbonization; Add the 2.9mL0.005mol/L chloroplatinic acid aqueous solution behind the ultrasonic 1h of 180W, the ultrasonic dispersion of 180W 1h again, the pH value of conditioned reaction system is 9~10 then; This system is transferred in the microwave reactor, reacted 25min under 110 ℃ of conditions.After being cooled to room temperature; Through filtration, deionized water washing, oven dry; Obtain Pt-WC/ Graphene composite electrocatalyst (the theoretical negative carrying capacity of WC counts 20% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder, and the theoretical negative carrying capacity of Pt counts 5% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder);
(5) method of the preparation of working electrode is with reference to the step (5) of embodiment 1;
(6) the test job electrode and with the step (6) of commercial platinum C catalyst electrocatalysis characteristic comparative approach with reference to embodiment 1; Recording Pt-WC/ Graphene composite electrocatalyst is 728.5mA/mgPt to the peak current of methanol electro-oxidizing; Double the 311.7mA/mgPt of commercial platinum C catalyst, presentation of results Pt-WC/ Graphene eelctro-catalyst has higher methanol oxidation catalytic performance than commercial platinum C catalyst.