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 form differences, pattern is different, as active carbon, multi-walled carbon nano-tubes, SWCN etc. are used as electro-catalyst carrier, active carbon is wherein widely used in fuel-cell catalyst carrier, and CNT has also obtained research and development widely as carrier.But the catalyst of preparing take above-mentioned material with carbon element as carrier has mostly used a large amount of noble metal platinums, cause catalyst cost too high, and their catalytic activity is not very high, easily reunite, cause stability also to have certain problem.
The problem existing in order to overcome above-mentioned catalyst, researchs and develops a kind of new eelctro-catalyst, not only makes the cost of catalyst significantly reduce, and the utilization rate of noble metal platinum is improved, and makes its electrocatalysis characteristic strengthen simultaneously.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.The layer structure material with carbon element after graphite oxide reduction is referred to as grapheme material (RGO) by we, it has similarly a series of good peculiar character of single-layer graphene, specific area is higher, more Metal Supported position can be provided, simultaneously, Graphene shows very strong quantum effect and outstanding chemical stability, has superior machinery and Electronic Performance, can be used as a desirable template supported catalyst.
Tungsten carbide (WC) is a kind of crystal with hexagonal structure, has the characteristics such as high rigidity, high-wearing feature, high-melting-point, is widely used in the fields such as microbit, precision die and the 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 Electronic Structure of tungsten carbide and Pt is similar has an eka-platinium performance, has good catalytic activity as catalyst in some chemical reactions, is not subject to CO and the 1O of any concentration
-6the H of the order of magnitude
2s is poisoning, has good stability and anti-poisoning performance, and cheap, is a kind of catalyst that has development and application potentiality.Simultaneously tungsten carbide also has good electric conductivity, as application of electrode in the field such as electrochemical catalysis and fuel cell.There are some researches show, although the catalytic activity of tungsten carbide also has certain distance compared with pure platinum, but following tungsten carbide substitutes (the Daniel V.Esposito that has a high potential of platinum, Jingguang G.Chen, 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, take Graphene as catalyst carrier, by tungsten carbide nanoparticulate dispersed in graphene sheet layer structure, the WC/RGO of preparation again in load nanometer Pt particle synthesize Pt-WC/RGO composite catalyst and should there is good electrocatalysis characteristic, especially for anodic oxidation of methanol.
(3) summary of the invention
The object of the invention is to provide a kind of Pt-WC/ Graphene composite electrocatalyst and preparation method thereof, this catalyst is take Graphene as carrier, take tungsten carbide and a small amount of platinum as double activated component, the method substep preparation combining by dipping reduction and carbonization and heating using microwave liquid phase coreduction, realize the even controllable load of active particle on RGO surface, show by Electrochemical Detection, this catalyst can significantly improve the catalytic performance to methanol electro-oxidizing.
The technical solution used in the present invention is:
A kind of Pt-WC/ Graphene composite electrocatalyst, described catalyst is take Graphene as carrier, and take tungsten carbide (WC) and platinum (Pt) as active component, the load capacity of tungsten carbide is 10~50%, and the load capacity of platinum is 5~10%.
Further, described catalyst is take Graphene as carrier, and take tungsten carbide and platinum as active component, the load capacity of tungsten carbide is preferably 10~30%, and the load capacity of platinum is preferably 5~8%.
The invention provides a kind of method of the Pt-WC/ of preparation Graphene composite electrocatalyst, described method is: graphite oxide be impregnated in ammonium metatungstate aqueous solution, obtain mixed liquor, fully dry after dipping, obtain ammonium metatungstate/graphite oxide powder, again take CO as reduction and carbonization gas, ammonium metatungstate in 400~900 ℃ of procedural heating reduction carbonization ammonium metatungstate/graphite oxide powder, obtain tungsten carbide/graphite oxide powder, in tungsten carbide/graphite oxide powder, add ethylene glycol again, after ultrasonic dispersion, add chloroplatinic acid aqueous solution, heating using microwave to 100~120 ℃, reaction 15~25min, reactant liquor after filtration, deionized water washing, dry, obtain Pt-WC/ Graphene composite electrocatalyst, 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, described ethylene glycol volumetric usage is counted 0.29~0.77ml/mg with tungsten carbide/graphite oxide powder quality, the volumetric usage of described chloroplatinic acid aqueous solution is counted 0.02~0.12ml/mg with tungsten carbide/graphite oxide powder quality, the molar concentration of described chloroplatinic acid aqueous solution is 0.005mol/L, the intake of described CO is 100ml/min, in described mixed liquor, the content of graphite oxide is 10.6~19.7mg/ml mixed liquor, preferably 10.64~19.74mg/ml mixed liquor, the content of described ammonium metatungstate is 1.5~10.4mg/ml mixed liquor, preferably 1.52~10.44mg/ml mixed liquor.
Further, described Pt-WC/ Graphene composite electrocatalyst preparation method is as follows:
1) preparation of graphite oxide (GO): graphite powder and concentrated sulfuric acid solution are mixed, stir in ice bath after 30min, slowly add KMnO
45~15 ℃ of reaction 2h, stir 40min at 30~40 ℃ again, slowly add deionized water A, 95~100 ℃ of reaction 1h, more slowly add the hydrogen peroxide that deionized water B and mass fraction are 30%, naturally cool to that to add mass concentration after room temperature be 18% aqueous hydrochloric acid solution, by centrifugal above-mentioned reactant liquor, precipitate with deionized water washing, dry, obtain graphite oxide powder; Described graphite powder and KMnO
4mass ratio be 1: 3, described concentrated sulfuric acid volumetric usage is 23ml/g graphite powder, the volumetric usage of described hydrogen peroxide is 30ml/g graphite powder, the volumetric usage of described aqueous hydrochloric acid solution is 14ml/g graphite powder, the volumetric usage of described deionized water A is 50ml/g graphite powder, and the volumetric usage of described deionized water B is 20ml/g graphite powder;
2) be dispersed in ammonium metatungstate aqueous solution ultrasonic graphite oxide, fully mix, obtain mixed liquor, 85 ℃ are stirred evaporate to dryness mixed liquor, obtain ammonium metatungstate/graphite oxide powder; In described mixed liquor, the content of graphite oxide is 10.6~19.7mg/ml mixed liquor, and the content of described ammonium metatungstate is 1.5~10.4mg/ml mixed liquor, and the concentration of described ammonium metatungstate aqueous solution is generally 1.6~11.9mg/ml; In described mixed liquor, the mass ratio of graphite oxide and ammonium metatungstate is 1.9~7.3;
3) ammonium metatungstate (AMT)/graphite oxide powder is put into high-temperature tubular carbide furnace, take CO as reduction and carbonization gas, adopt temperature-programmed mode reduction and carbonization ammonium metatungstate, obtain tungsten carbide (WC)/graphite oxide powder; The theoretical negative carrying capacity of described tungsten carbide counts 10~30% with graphite oxide quality; The intake of CO is 100ml/min;
4) in tungsten carbide/graphite oxide powder, add ethylene glycol (EG), after the ultrasonic dispersion of 180W, add chloroplatinic acid aqueous solution, 180W is ultrasonic is again uniformly dispersed, regulate between pH value 9~10, heating using microwave to 100~120 ℃ reaction 15~25min, after reactant liquor is cooling, through filtration, deionized water washing, oven dry, obtain Pt-WC/ Graphene composite electrocatalyst; Described ethylene glycol volumetric usage is counted the volumetric usage of 0.29~0.77ml/mg, described 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 described chloroplatinic acid aqueous solution is 0.005mol/L; The theoretical negative carrying capacity of described platinum counts 5~8% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder.
Described temperature-programmed mode reduction and carbonization ammonium metatungstate carries out as follows: first the lasting 30min of logical N2 removes tubular type furnace air, adopting CO is reduction and carbonization gas, vacuum tube furnace 30min is set and is warming up to 400 ℃ of maintenance 1h, then 30min is warming up to 900 ℃ of maintenance 4h, and reduction and carbonization ammonium metatungstate obtains WC/GO powder.
The volumetric usage of described chloroplatinic acid aqueous solution is preferably 0.049~0.062ml/mg in tungsten carbide/graphite oxide quality.
The preparation method of graphite oxide of the present invention is with reference to Fu Ling, Liu Hongbo, and Zou Yanhong, Li Bo, Hummers legal system affects the technological factor research [J] of degree of oxidation, charcoal element, 2005,4 (124): 10-14 during for graphite oxide).
Deionized water A of the present invention and deionized water B are deionized water, name for ease of distinguishing the statement of different step.
The present invention is first by being dispersed in graphite oxide powder in ammonium metatungstate aqueous solution, dipping evaporating water obtains AMT/GO, in vacuum tube furnace, reduction and carbonization obtains tungsten carbide/graphite oxide (WC/GO) again, and then prepares Pt-WC/RGO take it as carrier.Have the following advantages like this:
(1) ammonium metatungstate can well be water-soluble, water is cooked solvent and has also avoided the introducing of impurity (saved and removed the trouble that impurity brings), and graphite oxide has abundant hydrophily oxygen-containing functional group, as 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 load site with these functional groups, for the nucleation of WC below provides advantage, also play good peptizaiton simultaneously;
(2) carbonisation is below to adopt temperature programming control, also goes up to a certain degree the reunion that can avoid WC particle;
(3) the synthetic Pt-WC/RGO of substep can effectively avoid platinum grain that self reunion occurs, and is conducive to 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 size are controlled, WC used is cheap and possess some row excellent chemical character, as can significantly reducing eelctro-catalyst cost for platinum catalyst, improve its catalytic performance simultaneously, be expected to accelerate the paces of fuel cell commercialization.
(4) accompanying drawing explanation
Fig. 1 is Pt-WC/ Graphene composite electrocatalyst preparation flow figure
Fig. 2 is the scanning electron microscope (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 described WC and Pt is all take the quality of GO as benchmark.
The scanning electron microscope (SEM) photograph (SEM) of graphite oxide, adopts Hitachi S4700 type field emission scanning electron microscope (Japanese Hitachi company) test.
The transmission electron microscope picture (TEM) of graphite oxide, 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): by the dense H of 1g graphite powder (spectroscopic pure, traditional Chinese medicines group) and 23mL 98%
2sO
4solution mixes, and in ice bath, after mechanical agitation 30min, slowly adds 3g KMnO
4, keep 10 ± 5 ℃ of temperature to continue to stir 2h.Then transfer them in water bath with thermostatic control, keep 35 ± 5 ℃ of temperature to continue to stir 40min, after end, slowly add 50mL deionized water, temperature maintains 95~100 ℃, and reaction 1h, then slowly adds 20mL deionized water, slowly add again 30mL 30% hydrogen peroxide, after naturally cooling to room temperature, add 14mL 18% hydrochloric acid solution, by the centrifugal 10min of above-mentioned reactant liquor 3000rpm, precipitate with deionized water obtains graphite oxide powder 1.5g after washing, being dried; Graphite oxide scanning electron microscope (SEM) photograph (SEM) and transmission electron microscope picture (TEM) are shown in shown in Fig. 2 and Fig. 3;
(2) 32.3mg ammonium metatungstate is dissolved in 20mL deionized water, add 236.5mg graphite oxide (GO) powder, ultrasonic being uniformly dispersed, obtain 21.3mL mixed liquor, this mixture is transferred in oil bath pan, 85 ℃ of reaction temperatures are set, stir on dipping limit, limit, until the whole moisture of evaporate to dryness obtains AMT/GO powder 268mg;
(3) by dry AMT/GO powder transfer to quartz boat, be put in vacuum tube furnace (OTF-1200X, Hefei Ke Jing Materials Technology Ltd.) inner, adopt CO as carbonizing reduction gas, gas flow is 100ml/min, vacuum tube furnace 30min is set and is warming up to 400 ℃ and keep 1h, then 30min is warming up to 900 ℃ and keeps 4h, AMT is all reduced carbonization and obtains WC/GO powder with this understanding, and the theoretical negative carrying capacity of described tungsten carbide counts 10% with graphite oxide quality;
(4) above-mentioned WC/GO powder cooling after, after getting 61.0mg carbonization, WC/GO powder (GO Theoretical Mass 54.9mg) adds 20mL ethylene glycol in microwave reaction pipe, after the ultrasonic 1h of 180W, add 3.0mL 0.005mol/L chloroplatinic acid aqueous solution, the ultrasonic dispersion of 180W 1h again, then the pH value that regulates reaction system is 9~10, this system is transferred in microwave reactor, under 100 ℃ of conditions, reacted 15min.Be cooled to after room temperature, deionized water washing after filtration,, oven dry, obtain Pt-WC/ Graphene composite electrocatalyst (the theoretical negative carrying capacity of WC is counted the theoretical negative carrying capacity of 10%, Pt and counted 5% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder); Tungsten carbide/graphite oxide (WC/GO) transmission electron microscope picture is shown in Fig. 4; The TEM of Pt-WC/ Graphene composite electrocatalyst schemes as shown in Figure 5; The X-ray energy spectrum (EDS) of Pt-WC/ Graphene composite electrocatalyst as 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 ul-trasonic irradiation, drip and be coated on glassy carbon electrode with the liquid-transfering gun mixed serum that takes a morsel, naturally dry rear as measuring working electrode; And catalyst in contrast take commercial platinum carbon (mass fraction of Pt is as 20%, Johnson Matthey);
(6) test job electrode and with the comparison of commercial platinum C catalyst electrocatalysis characteristic: measure the three-electrode system of employing standard, large area platinized platinum is to electrode, and saturated calomel electrode (SCE) is reference electrode, and electrolyte is 0.5mol/L H
2sO
4+ 1.0mol/L CH
3oH solution.Evaluate eelctro-catalyst to Electrocatalytic Oxidation of Methanol activity by 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 to 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) 238mg ammonium metatungstate is dissolved in 20mL deionized water, add 450mg graphite oxide (GO) powder, ultrasonic being uniformly dispersed, obtain 22.8mL mixed liquor, this mixed liquor is transferred in oil bath pan, 85 ℃ of reaction temperatures are set, stir on dipping limit, limit, until the whole moisture of evaporate to dryness obtains AMT/GO powder 672mg;
(3) preparation method of WC/GO is with reference to the step (3) of embodiment 1;
(4) after cooling, after getting 26.0mg carbonization, WC/GO powder (Theoretical Mass of GO is 18.2mg) adds 20mL ethylene glycol in microwave reaction pipe, after the ultrasonic 1h of 180W, add 1.6mL0.005mol/L chloroplatinic acid aqueous solution, the ultrasonic dispersion of 180W 1h again, then the pH value that regulates reaction system is 9~10, this system is transferred in microwave reactor, under 120 ℃ of conditions, reacted 20min.Be cooled to after room temperature, deionized water washing after filtration,, oven dry, obtain Pt-WC/ Graphene composite electrocatalyst (the theoretical negative carrying capacity of WC is counted the theoretical negative carrying capacity of 30%, Pt and counted 8% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder 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) 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) 69.0mg ammonium metatungstate is dissolved in 20mL deionized water, add 224.5mg graphite oxide powder, ultrasonic being uniformly dispersed, obtain mixture 21.1ml, this mixed liquor is transferred in oil bath pan, 85 ℃ of set temperatures, stir on dipping limit, limit, until the whole moisture of evaporate to dryness obtains AMT/GO powder 291mg;
(3) preparation method of WC/GO is with reference to the step (3) of embodiment 1;
(4) after cooling, after getting 67.0mg carbonization, WC/GO powder (Theoretical Mass of GO is 53.6mg) adds 20mL ethylene glycol in microwave reaction pipe, after the ultrasonic 1h of 180W, add 2.9mL0.005mol/L chloroplatinic acid aqueous solution, the ultrasonic dispersion of 180W 1h again, then the pH value that regulates reaction system is 9~10, this system is transferred in microwave reactor, under 110 ℃ of conditions, reacted 25min.Be cooled to after room temperature, deionized water washing after filtration,, oven dry, obtain Pt-WC/ Graphene composite electrocatalyst (the theoretical negative carrying capacity of WC is counted the theoretical negative carrying capacity of 20%, Pt and counted 5% with the Theoretical Mass of graphite oxide in tungsten carbide/graphite oxide powder 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) 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.