A kind of method and its application preparing metal-carbon composite catalyzing materialTechnical field
The present invention relates to a kind of method and its application for preparing metal-carbon composite catalyzing material, belong to carbon-based material preparationTechnical field.
Background technique
C-based nanomaterial because it has excellent electric conductivity and thermal conductivity, good mechanical property and high-specific surface area,Many advantages, such as price of the structure and active site abundant and relative moderate that are easy to regulate and control, in recent years in energy storage,Heterogeneous catalysis and environmental protection etc. get more and more people's extensive concerning.Importantly, having unique physicochemical property and being easy toThe carbon nanomaterial of regulation easily can adjust its superficiality by introducing intrinsic defect, foreign atom and functional groupMatter, this provides opportunity further to rationally design advanced c-based nanomaterial, and will be helpful to more fully understand structure-performanceBetween relationship.Recent research indicate that the research emphasis for adulterating carbon material is mainly mixed with nitrogen-doped carbon (N-C material) and metal nitrogenBased on miscellaneous carbon (M-N-C).Especially this kind of metal-carbon composite (M-N-C) has both many excellent of metal and nitrogen-doped carbon materialPoint and the " MN containing catalytic activityX" site, with corproporphyrin structure, monometallic site therein can also be directly as workProperty site, this kind of material has maximum atom utilization, homogeneous catalyst active site, lower metal ligancy and vulnerable to tuneThe advantages such as the electronic structure of control show the catalytic property dramatically different with corresponding block materials, in water-splitting, metal-airBattery and conventional multiphase catalytic field show biggish application prospect.However, the system of this kind of metal-carbon composite nano materialsIt is standby, it usually needs using metal organic framework compound or organic micromolecule compound and organic polymer as presoma, to lead toCross high-temperature roasting preparation；Or it is obtained using the reduction of wet chemistry method dipping.So during the preparation process, inevitably needing phaseWhen the solvent (such as the auxiliary agents such as the organic agents such as alcohol or acid-base reagent and surfactant) of quantity, no matter using organic moltenAgent/auxiliary agent reagent or acid-base reagent, this will necessarily generate a large amount of waste liquids, will increase environmental pressure and manufacturing cost, seriously violateGreen chemical concept greatly limits its prepare with scale and industrial application prospect.Therefore, it is necessary to a kind of green is developed,Low cost, convenient and large-scale production method prepare the high-quality metal-carbon composite with good form to meetFollowing application demand.
Summary of the invention
In order to overcome the deficiencies in the prior art, metal-carbon composite catalyzing is prepared it is an object of the present invention to provide a kind ofThe method and its application of material.This method simple process, it is with short production cycle, at low cost, environmentally protective, be capable of large scale preparationCategory-carbon composite.Using this method preparation metal-carbon composite have metal nanoparticle size is small, impurity is less,The advantages that catalytic activity is high, active material is stablized has biggish application potential in catalytic field, and has probed into composite material and existedCatalytic activity in water decomposition and carbon dioxide reduction reaction.
In order to achieve the above-mentioned object of the invention, in the presence of solving the problems, such as prior art, technical solution that the present invention takesIt is: a method of preparing metal-carbon composite catalyzing material, comprising the following steps:
Step 1, by 0.5-5g carbon source and 0.02-1g metal salt, mixing is placed in the ball grinder of 50mL zirconium oxide material, ball30-60min is ground, 1-20g nitrogen source, then ball milling 30-60min, the powder after obtaining ball milling are then added；The carbon source is selected from singleOne of peaceful acid, ellagic acid, Gallotannin, quercetin or ellagic tannin, the metal salt is selected from nickel acetate, sulphurOne of sour copper, cobalt acetate, ferric nitrate, zinc chloride, manganese nitrate, silver acetate, acetic acid gold or palladium acetate, the nitrogen source is selected from doubleCyanamide, one of urea or melamine；
Step 1 is obtained the powder after ball milling by step 2, is placed in tube furnace, under protection of argon gas, 600-1000 DEG C of roasting1-2h is burnt, metal-carbon composite catalyzing material is made.
The metal-carbon composite catalyzing material of the method preparation is catalyzed reaction in water decomposition and in carbon dioxide electrificationLearn the application in reduction catalysts reaction.
The medicine have the advantages that a kind of method and its application for preparing metal-carbon composite catalyzing material, wherein the side of preparationMethod is the following steps are included: 0.5-5g carbon source and 0.02-1g metal salt are mixed the ball grinder for being placed in 50mL zirconium oxide material by (1)In, then ball milling 30-60min adds 1-20g nitrogen source, then ball milling 30-60min, the powder after obtaining ball milling；(2) by step1 obtains the powder after ball milling, is placed in tube furnace, and under protection of argon gas, it is multiple that metal-carbon is made in 600-1000 DEG C of roasting 1-2hClose catalysis material.Using the metal-carbon composite of this method preparation with metal nanoparticle size is small, impurity is less, urgesChange the advantages that activity is high, active material is stablized, there is biggish application potential in catalytic field, and probed into composite material in waterIt decomposes and the catalytic activity in carbon dioxide reduction reaction.It is the method for the present invention simple process, with short production cycle, at low cost, greenEnvironmental protection, being capable of large scale preparation metal-carbon composite catalyzing material.
Detailed description of the invention
Fig. 1 is the X-ray diffraction analysis figure of the Ni-N-C catalyst prepared in embodiment 1.
Fig. 2 is the transmission electron microscope photo figure of the Ni-N-C catalyst prepared in embodiment 2.
In figure: (a) high power that scale is 50nm projects electron microscope, and (b) high power that scale is 20nm projects electron microscope.
Fig. 3 is the X-ray diffraction analysis figure of the Pd-N-C catalyst prepared in embodiment 10.
Fig. 4 is the performance map of Carbon dioxide electrochemical reduction described in embodiment 11.
Fig. 5 is (0.5M H in acid condition described in embodiment 122SO4) liberation of hydrogen polarization curve.
Fig. 6 is (0.5M H in acid condition described in embodiment 132SO4) analysis oxygen polarization curve.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Embodiment 1
0.5g tannic acid and 0.1g nickel acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 30min adds 1g melamine, then ball milling 30min.Then the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 700 DEG C of roasting 1h can be prepared by Ni-N-C c-based nanomaterial catalyst.From the XRD diagram (figure of sample1) it will be clear that (002) characteristic diffraction peak of carbon, does not occur the characteristic diffraction peak of apparent elemental nickel in.
Embodiment 2
1g ellagic acid and 0.5g nickel acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 30min adds 3g dicyandiamide, then ball milling 30min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 800 DEG C of roasting 2h can be prepared by Ni-N-C c-based nanomaterial catalyst.From the transmission electron microscope of sampleIt can be seen that material has pore structure abundant in photo figure (Fig. 2), it is applied to electrochemically reducing carbon dioxide and showsExcellent catalytic activity.
Embodiment 3
5g tannic acid and 1g copper sulphate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 60min adds 20g dicyandiamide, then ball milling 60min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 800 DEG C of roasting 2h can be prepared by Cu-N-C c-based nanomaterial catalyst.
Embodiment 4
2g Gallotannin and 0.3g cobalt acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball30min is ground, 5g urea, then ball milling 30min are then added.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 600 DEG C of roasting 1h can be prepared by Co-N-C c-based nanomaterial catalyst.It is applied to acid itemElectrolysis water liberation of hydrogen under part shows relatively excellent catalytic activity.
Embodiment 5
1g tannic acid and 0.1g ferric nitrate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 30min adds 10g melamine, then ball milling 40min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tubular typeIn furnace, under protection of argon gas, 900 DEG C of roasting 1h can be prepared by Fe-N-C c-based nanomaterial catalyst.It is applied to acidityUnder the conditions of be electrolysed elutriation oxygen, show relatively excellent catalytic activity.
Embodiment 6
3g quercetin and 1g zinc chloride are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 45min adds 6g melamine, then ball milling 45min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 1000 DEG C of roasting 1.5h can be prepared by Zn-N-C c-based nanomaterial catalyst.
Embodiment 7
2g tannic acid and 0.5g manganese nitrate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 45min adds 6g melamine, then ball milling 45min.Then, by the obtained powder after above-mentioned ball milling, it is placed in tubular typeIn furnace, under protection of argon gas, 850 DEG C of roasting 2h can be prepared by Mn-N-C c-based nanomaterial catalyst.
Embodiment 8
0.5g tannic acid and 0.03g silver acetate are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 50min adds 8g melamine, then ball milling 30min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 800 DEG C of roasting 1h can be prepared by Ag-N-C c-based nanomaterial catalyst.
Embodiment 9
0.5g tannic acid and 0.02g acetic acid gold are weighed respectively, and mixing is placed in the ball grinder of 50mL zirconium oxide material, ball millingThen 40min adds 8g melamine, then ball milling 50min.Then, the powder that will be obtained after above-mentioned ball milling, is placed in tube furnaceIn, under protection of argon gas, 950 DEG C of roasting 1h can be prepared by Au-N-C c-based nanomaterial catalyst.
Embodiment 10
0.5g ellagic tannin and 0.03g palladium acetate are weighed respectively, and mixing is placed in the ball milling of 50mL zirconium oxide materialIn tank, then ball milling 35min adds 5g melamine, then ball milling 55min.Then, the powder that will be obtained after above-mentioned ball milling,It is placed in tube furnace, under protection of argon gas, 800 DEG C of roasting 2h can be prepared by Pd-N-C c-based nanomaterial catalyst.From sampleXRD diagram (Fig. 3) in it will be clear that carbon (002) characteristic diffraction peak, do not occur the feature diffraction of apparent simple substance palladiumPeak.
Embodiment 11
Electrochemically reducing carbon dioxide performance test, electrochemistry used are carried out to prepared metal-carbon composite catalystWork station is Shanghai Chen Hua CHI660E.Electrolytic cell is H-type, is proton exchange membrane, 0.1M NaHCO with nafion 1173AsElectrolyte is to electrode, using the conductive carbon paper that catalyst loads as work with platinized platinum using silver/silver chloride electrode as reference electrodeMake electrode, constitutes three-electrode system.Electrochemically reducing carbon dioxide performance test is carried out with catalyst prepared by embodiment 2,Catalyst prepared by 5mg is taken, is dissolved in 1mL ethyl alcohol, is then added 30 μ L nafion binders, after ultrasonic 30min, takes 100μ L is coated on 1cm-2On carbon paper, excellent carbon dioxide reduction performance is shown after drying at room temperature as working electrode ,-Under 0.86V voltage, carbon monoxide faradic efficiency is up to 94.8%, shows excellent performance as shown in figure 4, current densityUp to 18.2mA cm-2, and have excellent stability, it can be steady testing 25 hours.
Embodiment 12
Carrying out electrolysis water liberation of hydrogen to prepared metal-carbon composite catalyst can test, and electrochemical workstation used is upperHai Chenhua CHI660E.Electrolytic cell is there-necked flask shape, 0.5M H2SO4As electrolyte, using silver/silver chloride electrode as reference electrode,It is that using the conductive carbon paper that catalyst loads as working electrode, three-electrode system is constituted to electrode with carbon-point.With 4 institute of embodimentThe catalyst of preparation, which carries out electrolysis water liberation of hydrogen, to be tested, and take catalyst prepared by 2mg, be dissolved in 1mL ethyl alcohol, be then added 30μ L nafion binder after ultrasonic 30min, takes 20 μ L to be coated on 0.2cm-2On carbon paper, after drying at room temperature as working electrode intoThe test of row Hydrogen Evolution Performance, shows relatively excellent performance, can obtain from its liberation of hydrogen polarization curve (LSV, Fig. 5), reach 10mAcm-2Its overpotential of current density is only 34mV.
Embodiment 13
Electrolysis elutriation oxygen performance test is carried out to prepared metal-carbon composite catalyst, electrochemical workstation used isShanghai Chen Hua CHI660E.Electrolytic cell is there-necked flask shape, 0.5M H2SO4As electrolyte, using silver/silver chloride electrode as reference electricityPole is, using the conductive carbon paper that catalyst loads as working electrode, to constitute three-electrode system to electrode with carbon-point.With embodiment 5Prepared catalyst, which carries out electrolysis elutriation oxygen, to be tested, and take catalyst prepared by 2mg, be dissolved in 1mL ethyl alcohol, be then added30 μ L nafion binders after ultrasonic 30min, take 20 μ L to be coated on 0.2cm-2On carbon paper, working electrode is used as after drying at room temperatureAnalysis oxygen performance test is carried out, relatively excellent performance is shown, analysing oxygen polarization curve (LSV, Fig. 6) from it can obtain, and reach 10mAcm-2Its overpotential of current density is 480mV.