WO2016027123A1 - A method for producing non-precious metal catalysts from nitrogen-rich biomass - Google Patents
A method for producing non-precious metal catalysts from nitrogen-rich biomass Download PDFInfo
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- WO2016027123A1 WO2016027123A1 PCT/IB2014/063945 IB2014063945W WO2016027123A1 WO 2016027123 A1 WO2016027123 A1 WO 2016027123A1 IB 2014063945 W IB2014063945 W IB 2014063945W WO 2016027123 A1 WO2016027123 A1 WO 2016027123A1
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- precious metal
- nitrogen
- treating
- metal catalysts
- acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 49
- 239000010970 precious metal Substances 0.000 title claims abstract description 32
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 21
- 239000002028 Biomass Substances 0.000 title claims abstract description 12
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title description 28
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 239000002253 acid Substances 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 150000001722 carbon compounds Chemical class 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 6
- 239000011261 inert gas Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- 238000000498 ball milling Methods 0.000 claims abstract description 3
- 238000001354 calcination Methods 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 16
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 210000000988 bone and bone Anatomy 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005539 carbonized material Substances 0.000 claims description 2
- 235000013372 meat Nutrition 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 16
- 239000003575 carbonaceous material Substances 0.000 description 13
- 239000000843 powder Substances 0.000 description 13
- 241000894007 species Species 0.000 description 13
- 239000000047 product Substances 0.000 description 11
- 229910052742 iron Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 230000009467 reduction Effects 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 235000015278 beef Nutrition 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000197 pyrolysis Methods 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229940032296 ferric chloride Drugs 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- 241000143432 Daldinia concentrica Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000287828 Gallus gallus Species 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical class [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 description 1
- 150000001720 carbohydrates Chemical group 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229940044631 ferric chloride hexahydrate Drugs 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000004050 hot filament vapor deposition Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 description 1
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- -1 particularly Polymers 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/06—Washing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Definitions
- the present invention relates to a method for producing non-precious metal catalysts from nitrogen-rich biomass in the field of composite material technology.
- the present invention relates to a method for producing non- precious metal catalysts from nitrogen-rich biomass for oxygen reduction reaction, as well as the applications of the resulting non-precious metal oxygen reduction catalyst materials, e.g. in fuel cell.
- PEFC Polymer electrolyte fuel cells
- Non- precious metal based catalyst materials have been emerging as competitive replacements due to recent improvements with respect to their ORR activity and operational stability, with the most extensively studied non-precious catalysts to date generally consisting of Fe and/or Co species, coordinated to nitrogen-carbon complexes.
- the highest performing catalysts of this type are generally prepared by high temperature pyrolysis of a carbon support in the presence of transition metal species (usually inorganic salts or macrocycle complexes) and a nitrogen precursor source.
- the nitrogen source generally consists of simple inorganic molecules such as ethylenediamine, 1 ,10-phenanthroline, pyridine and polyacrylonitrile.
- N-containing carbon materials have high methanol/CO tolerance, outstanding durability, and relatively high electrocatalytic activity.
- the high catalytic activity of N-doped carbon may relate to the larger electronegativity of N in contrast to C atoms. Theoretically, N atoms may create positive charge density on adjacent C atoms, thus being favorable for the adsorption of O2 and subsequent electrocatalytic activity of carbon materials.
- N-doped carbons hold relatively high electrocatalytic activity, much room for improvement remains especially in acid conditions.
- transition metal e.g. Co and Fe
- series of metal-nitrogen-carbon catalyst were prepared, in which the best catalyst exhibited a current density of 105 imA cm 2 at 0.80 V in H2/O2 fuel cell testing.
- Fe nanoparticles inserted nitrogen-doped carbon nanotubes were also prepared, which not only displays the highest oxygen reduction reaction activity in alkaline media of any non-precious metal catalysts but also outperforms the most active platinum-based catalysts when used at a sufficiently high loading.
- N-doped carbon materials can be grown from nitrogen-containing precursors by catalytic chemical vapor deposition.
- Thermal treatment under Nhh atmosphere is another commonly used method for doping carbon materials with nitrogen.
- Plasma treatment under nitrogen atmosphere was studied and found to be effective in producing N-doped carbon materials.
- Nitrogen-containing polymers, particularly, polyaniline was coated on carbon materials and the obtained composite was thermally treated under an inert atmosphere to get nitrogen-doped carbon materials.
- the high heat treatment temperature makes lots of N- active sites lost, which limits the capability of these catalyst materials. Therefore, finding an appropriate way for effectively doping N to carbon materials is very important to develop non-precious metal and/or metal-free catalysts for ORR.
- Carbon nanotubes containing nitrogen were obtained by pyrolysis of iron (II) phatolcyannine followed by complete removal of the residual Fe catalyst. (US2010183950) or by double temperature pyrolysis where solid carbon source and nitrogen source precursors are sublimated in a low temperature zone and deposited on a carbon nanotube in a high temperature zone (CN 102416337)
- Nitrogen doped hollow carbon balls were obtained by high temperature pyrolysis of poly (o-phenylenediamine) hollow balls (CN 102891326)
- the object of the present invention is to provide a method for producing non- precious metal catalysts from nitrogen-rich biomass for oxygen reduction reaction. Another object of the present invention is to provide novel oxygen reduction catalyst materials by using the presented method.
- a method for producing non-precious metal catalysts from N-rich biomass which includes processing a precursor compound containing C, N, P, H and O elements by means of the following sequential steps:
- the precursor compound may contain C, H, N, P and O biomass.
- the precursor compound may be derived from meat and bone.
- the acid may be HNO3, H 2 SO4, HCI and/or H3PO4.
- the Fe species may be FeC .
- Step (b) may be conducted at a temperature of 300-1000 °C.
- Step (e) may be conducted at a temperature of 25-100 °C.
- the N atoms in the precursor compounds may be doped into the structure of the final carbon compound.
- the carbonized material of step (b) may be used for oxygen reduction reaction.
- a non-precious metal catalyst material as produced by the method as described herein.
- the metal material may be used in fuel cells.
- the heating time may be in the range of 10 min to 24 hr.
- Fe species such as ferric chloride (FeC ) may be dissolved in water, into which the final product from step (a) is added with stirring, and then dried.
- FeC ferric chloride
- the dried sample may be ball-milled again.
- the mixture may be heat-treated at high temperature under inert gas atmosphere.
- the obtained powder may be immersed in acid solution, then washed with deionized water until pH of filtrate was neutral and dried.
- This process may be conducted at 400-1000 °C under inert gas atmosphere.
- the heating time may be in the range of 10 min to 24 hr.
- the drying process may be conducted at 25-100 °C.
- the invention also extends to non-precious metal catalysts as produced by the method as set out above.
- the non-precious metal catalysts in accordance with the invention may be used in fuel cells.
- Figure 1 SEM image of the non-precious metal catalysts obtained from carbonization at 700 °C;
- Figure 2 SEM image of the non-precious metal catalysts obtained from carbonization at 800 °C;
- Figure 3 XRD patterns of the non-precious metal catalysts before and after high temperature carbonization
- Figure 5 Polarization curves of the non-precious metal catalysts and the commercial XC-72 carbon powder for oxygen reduction.
- the non-precious metal catalysts prepared by means of the present invention were physical characterized and tested for oxygen reduction performance.
- Figure 1 and Figure 2 show the SEM images of the non-precious metal catalysts after high temperature carbonization. It can be seen that the catalyst material presented a uniform massive structure after carbonization at high temperature, which means the carbohydrate units in the precursor compound were basically carbonized at high temperature; accordingly the nitrogen in precursors can be doped into the structure of resulted carbon materials.
- Figure 3 shows the XRD patterns of the non-precious metal catalysts and the sample after FeC treatment, from which it can be seen that the material was graphitized after high temperature carbonization and unstable Fe species can be completely removed by acid.
- Figure 4 shows the Raman spectra of the non-precious metal catalysts made from beef and bone. Two characteristic peaks of carbon structural materials, namely D band and G band, are observed at -1308 cm 1 and -1593 cm 1 respectively in both samples, which means that the catalyst material formed a typical carbon material structure.
- Figure 5 shows the polarization curves of the non-precious metal catalyst made by this method and the commercial XC-72 carbon powder for oxygen reduction. It is clear that the ORR onset potential and half-wave potential for the novel metal- free oxygen reduction catalyst material is 123 mV and 79 mV more positive than those for the commercial XC-72 carbon powder, respectively, indicating that this material has better performance than the traditional commercial XC-72 carbon powder on ORR.
- the present invention assists in avoiding the N loss problem resulting from the traditional high temperature heat treatment process, improved the integration of C and N species in the novel non-precious metal oxygen reduction catalyst material, and promoted the catalytic performance of the reactive N species for ORR, which make the resulting catalysts has potential application in fuel cell field towards ORR.
- Example 1 Example 1 :
- the chicken bones were washed and then dried in a vacuum oven at 80 °C.
- the dried bones were smashed into small pieces and placed in a quartz tube furnace and then heated to 800 °C with a heating rate of 5 °C min "1 under N2 atmosphere and kept at 800 °C for 2 h.
- the obtained product was ball-milled at a speed of 250 rpm min 1 for 6 h, and then immersed into 2 M HNO3 solution for 24 hr with stirring at room temperature.
- the acid-treated product was filtered, washed with deionized water and dried at 60 °C. Then, the product was treated in 2 M HCI solution for 72 hr, washed and dried at 60 °C.
- Preparation of nitrogen-containing carbon was carried out by carbonizing fresh beef at high temperature in an inert gas tube furnace. 50 g of fresh beef was placed in a quartz tube furnace and then heated to 800 °C with a heating rate of 5 °C min 1 under N2 atmosphere and kept at 800 °C for 2 h. After the furnace cooled to room temperature, a black powder was obtained. The obtained powder was ball-milled for 6 h, and then immersed into 40 wt% HF solution for 2 h with stirring at room temperature. After that, the suspension was filtered, washed with deionized water and then heated at 800 °C for 2 h. Then, the black powder was added to 2 mol L 1 HNO3 solution stirred at 80 °C for 4 h.
- the black powder was rinsed and dried at 60 °C for 12 h.
- the resulting black powder was labeled as carbonized beef.
- the product was ball-milled with FeCb solution. The mixture was heated at 800 °C for 2 h under N2 atmosphere. In order to remove unstable iron species, the obtained powder was immersed in 2 M HNO3 solution again to remove unstable iron species. Finally, the product was filtered, washed and dried at 60 °C for 12 h.
- Glucose (4 g) and melamine (2 g) were mixed in a 400 ml beaker. After stirring thoroughly, concentrated sulfuric acid (10 ml) was added to the mixture drop by drop. Then, the resulting mixture was placed into an autoclave at 120 °C for 10 h for primary carbonization. The product was then pumping filtered, washed and dried. Finally, the product was further carbonized at high temperature (600 °C) in nitrogen atmosphere for 2 h. Subsequently, the black powder was rinsed and dried at 60 °C for 12 h. The resulting black powder was labeled as carbonized beef. Subsequently, the product was ball-milled with FeCb solution.
- the mixture was heated at 800 °C for 2 h under N2 atmosphere. In order to remove unstable iron species, the obtained powder was immersed in 2 M HNO3 solution again to remove unstable iron species. Finally, the product was filtered, washed and dried at 60 °C for 12 h
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a method for producing non-precious metal catalysts from N-rich biomass, which includes processing a precursor compound containing C, N, P, H and O elements by means of the following sequential steps: of drying and ball-milling; of heating at high temperature under inert gas atmosphere in a furnace to obtain carbonization; of treating in an acid to remove impurities; of treating with Fe species; of heating at high temperature in a nitrogen atmosphere to obtain calcination; and of treating in an acid to further remove impurities to a final carbon compound adapted to be non-precious metal catalyst.
Description
A METHOD FOR PRODUCING NON-PRECIOUS METAL CATALYSTS FROM
NITROGEN-RICH BIOMASS
FIELD OF INVENTION
The present invention relates to a method for producing non-precious metal catalysts from nitrogen-rich biomass in the field of composite material technology.
More particularly, the present invention relates to a method for producing non- precious metal catalysts from nitrogen-rich biomass for oxygen reduction reaction, as well as the applications of the resulting non-precious metal oxygen reduction catalyst materials, e.g. in fuel cell.
BACKGROUND TO INVENTION
Polymer electrolyte fuel cells (PEFC) have many advantages, such as high efficiency, no harmful gas emission, and low operation temperature for global environmental problems, and have been regarded as a promising clean energy conversion system for the next generation. The high cost and limited operational stability, however, still hinders the sustainable commercialization of this technology.
While Pt based materials are undeniably the highest performing oxygen reduction reaction (ORR) catalyst materials to date, their replacement by inexpensive alternatives is imperative in order to realize a potential fuel cell market. Non- precious metal based catalyst materials have been emerging as competitive replacements due to recent improvements with respect to their ORR activity and operational stability, with the most extensively studied non-precious catalysts to date generally consisting of Fe and/or Co species, coordinated to nitrogen-carbon complexes. The highest performing catalysts of this type are generally prepared by high temperature pyrolysis of a carbon support in the presence of transition
metal species (usually inorganic salts or macrocycle complexes) and a nitrogen precursor source. The nitrogen source generally consists of simple inorganic molecules such as ethylenediamine, 1 ,10-phenanthroline, pyridine and polyacrylonitrile.
N-containing carbon materials have high methanol/CO tolerance, outstanding durability, and relatively high electrocatalytic activity. The high catalytic activity of N-doped carbon may relate to the larger electronegativity of N in contrast to C atoms. Theoretically, N atoms may create positive charge density on adjacent C atoms, thus being favorable for the adsorption of O2 and subsequent electrocatalytic activity of carbon materials. However, while N-doped carbons hold relatively high electrocatalytic activity, much room for improvement remains especially in acid conditions. Combining transition metal (e.g. Co and Fe) and N doping into carbon materials has resulted in improved ORR performance. For instance, series of metal-nitrogen-carbon catalyst were prepared, in which the best catalyst exhibited a current density of 105 imA cm 2 at 0.80 V in H2/O2 fuel cell testing. In addition, Fe nanoparticles inserted nitrogen-doped carbon nanotubes were also prepared, which not only displays the highest oxygen reduction reaction activity in alkaline media of any non-precious metal catalysts but also outperforms the most active platinum-based catalysts when used at a sufficiently high loading.
An Fe and N-doped carbon catalyst of graphene structure was reported. In 0.1 M HCIO4 electrolyte, the ORR onset potential for the catalyst is high (up to 0.98 V) and the half-wave potential is only 60 mV less than that of the Pt/C catalyst. An iron-acetate/phenanthroline/zeolitic-imidazolate-framework-derived cathode electro-catalyst was also prepared, which, within a membrane electrode assembly, produced a peak power density of 0.91 W cm 2 and a power density of 0.75 W cm-2 at 0.6 V22. N configurations and the N content in N-doped carbon materials
play a crucial role in determining ORR performance. Transition metals may bond with N by way of adsorption and/or coordination, but the exact mechanistic basis for this enhancing effect remains unknown.
Different methods have been reported for doping carbon materials with nitrogen. N-doped carbon materials can be grown from nitrogen-containing precursors by catalytic chemical vapor deposition. Thermal treatment under Nhh atmosphere is another commonly used method for doping carbon materials with nitrogen. Plasma treatment under nitrogen atmosphere was studied and found to be effective in producing N-doped carbon materials. Nitrogen-containing polymers, particularly, polyaniline was coated on carbon materials and the obtained composite was thermally treated under an inert atmosphere to get nitrogen-doped carbon materials. However, the high heat treatment temperature makes lots of N- active sites lost, which limits the capability of these catalyst materials. Therefore, finding an appropriate way for effectively doping N to carbon materials is very important to develop non-precious metal and/or metal-free catalysts for ORR.
High temperature pyrolysis routes for obtaining nitrogen doped carbon for fuel cell catalysis applications were disclosed elsewhere:
Carbon nanotubes containing nitrogen were obtained by pyrolysis of iron (II) phatolcyannine followed by complete removal of the residual Fe catalyst. (US2010183950) or by double temperature pyrolysis where solid carbon source and nitrogen source precursors are sublimated in a low temperature zone and deposited on a carbon nanotube in a high temperature zone (CN 102416337)
Nitrogen doped hollow carbon balls were obtained by high temperature pyrolysis of poly (o-phenylenediamine) hollow balls (CN 102891326)
The object of the present invention is to provide a method for producing non- precious metal catalysts from nitrogen-rich biomass for oxygen reduction reaction.
Another object of the present invention is to provide novel oxygen reduction catalyst materials by using the presented method.
SUMMARY OF INVENTION
According to the invention, a method for producing non-precious metal catalysts from N-rich biomass, which includes processing a precursor compound containing C, N, P, H and O elements by means of the following sequential steps:
(a) of drying and ball-milling;
(b) of heating at high temperature under inert gas atmosphere in a furnace to obtain carbonization;
(c) of treating in an acid to remove impurities;
(d) of treating with Fe species;
(e) of heating at high temperature in a nitrogen atmosphere to obtain calcination; and
(f) of treating in an acid to further remove impurities to a final carbon compound adapted to be non-precious metal catalyst.
The precursor compound may contain C, H, N, P and O biomass.
The precursor compound may be derived from meat and bone.
The acid may be HNO3, H2SO4, HCI and/or H3PO4.
The Fe species may be FeC .
Step (b) may be conducted at a temperature of 300-1000 °C. Step (e) may be conducted at a temperature of 25-100 °C.
In step (e) the N atoms in the precursor compounds may be doped into the structure of the final carbon compound.
Step (e) may result in FexN (x=0.5-3) compounds formed on the surface of the final carbon compound.
The carbonized material of step (b) may be used for oxygen reduction reaction.
Also according to the invention, a non-precious metal catalyst material as produced by the method as described herein.
The metal material may be used in fuel cells.
The heating time may be in the range of 10 min to 24 hr.
Fe species, such as ferric chloride (FeC ) may be dissolved in water, into which the final product from step (a) is added with stirring, and then dried.
The dried sample may be ball-milled again.
Subsequently, the mixture may be heat-treated at high temperature under inert gas atmosphere.
In order to remove unstable iron species, the obtained powder may be immersed in acid solution, then washed with deionized water until pH of filtrate was neutral and dried.
This process may be conducted at 400-1000 °C under inert gas atmosphere. The heating time may be in the range of 10 min to 24 hr. The drying process may be conducted at 25-100 °C.
The invention also extends to non-precious metal catalysts as produced by the
method as set out above.
The non-precious metal catalysts in accordance with the invention may be used in fuel cells.
BRIEF DESCRIPTION OF DRAWINGS
The invention will now be described in reference to specific examples and the accompanying schematic drawings.
In the drawings there is shown in:
Figure 1 : SEM image of the non-precious metal catalysts obtained from carbonization at 700 °C;
Figure 2: SEM image of the non-precious metal catalysts obtained from carbonization at 800 °C;
Figure 3: XRD patterns of the non-precious metal catalysts before and after high temperature carbonization;
Figure 4: Raman spectras of the non-precious metal catalysts before and after high FeC treatment; and
Figure 5: Polarization curves of the non-precious metal catalysts and the commercial XC-72 carbon powder for oxygen reduction.
DETAILED DESCRIPTION OF DRAWINGS AND EXAMPLES
The non-precious metal catalysts prepared by means of the present invention were physical characterized and tested for oxygen reduction performance.
Figure 1 and Figure 2 show the SEM images of the non-precious metal catalysts after high temperature carbonization. It can be seen that the catalyst material
presented a uniform massive structure after carbonization at high temperature, which means the carbohydrate units in the precursor compound were basically carbonized at high temperature; accordingly the nitrogen in precursors can be doped into the structure of resulted carbon materials.
Figure 3 shows the XRD patterns of the non-precious metal catalysts and the sample after FeC treatment, from which it can be seen that the material was graphitized after high temperature carbonization and unstable Fe species can be completely removed by acid.
Figure 4 shows the Raman spectra of the non-precious metal catalysts made from beef and bone. Two characteristic peaks of carbon structural materials, namely D band and G band, are observed at -1308 cm 1 and -1593 cm 1 respectively in both samples, which means that the catalyst material formed a typical carbon material structure.
Figure 5 shows the polarization curves of the non-precious metal catalyst made by this method and the commercial XC-72 carbon powder for oxygen reduction. It is clear that the ORR onset potential and half-wave potential for the novel metal- free oxygen reduction catalyst material is 123 mV and 79 mV more positive than those for the commercial XC-72 carbon powder, respectively, indicating that this material has better performance than the traditional commercial XC-72 carbon powder on ORR.
In summary, the present invention assists in avoiding the N loss problem resulting from the traditional high temperature heat treatment process, improved the integration of C and N species in the novel non-precious metal oxygen reduction catalyst material, and promoted the catalytic performance of the reactive N species for ORR, which make the resulting catalysts has potential application in fuel cell field towards ORR.
Example 1 :
The chicken bones were washed and then dried in a vacuum oven at 80 °C. The dried bones were smashed into small pieces and placed in a quartz tube furnace and then heated to 800 °C with a heating rate of 5 °C min"1 under N2 atmosphere and kept at 800 °C for 2 h. After the furnace cooled to room temperature, the obtained product was ball-milled at a speed of 250 rpm min 1 for 6 h, and then immersed into 2 M HNO3 solution for 24 hr with stirring at room temperature. The acid-treated product was filtered, washed with deionized water and dried at 60 °C. Then, the product was treated in 2 M HCI solution for 72 hr, washed and dried at 60 °C. 1 g of ferric chloride (FeC ) was dissolved in 5 ml of ultrapure water, into which the obtained black product was added with stirring, and then dried at 90 °C. The dried sample was ball-milled for 6 h at 250 rpm. Subsequently, the mixture was heat-treated at 800 °C for 2 h under N2 atmosphere. In order to remove unstable iron species, the obtained powder was immersed in HNO3 solution (2 mol L"1) for 24 h with stirring, then washed with deionized water until pH of filtrate was neutral and dried at 60 °C for 12 h.
Example 2:
Preparation of nitrogen-containing carbon was carried out by carbonizing fresh beef at high temperature in an inert gas tube furnace. 50 g of fresh beef was placed in a quartz tube furnace and then heated to 800 °C with a heating rate of 5 °C min 1 under N2 atmosphere and kept at 800 °C for 2 h. After the furnace cooled to room temperature, a black powder was obtained. The obtained powder was ball-milled for 6 h, and then immersed into 40 wt% HF solution for 2 h with stirring at room temperature. After that, the suspension was filtered, washed with deionized water and then heated at 800 °C for 2 h. Then, the black powder was added to 2 mol L 1 HNO3 solution stirred at 80 °C for 4 h. Subsequently, the black powder was rinsed and dried at 60 °C for 12 h. The resulting black powder was
labeled as carbonized beef. Subsequently, the product was ball-milled with FeCb solution. The mixture was heated at 800 °C for 2 h under N2 atmosphere. In order to remove unstable iron species, the obtained powder was immersed in 2 M HNO3 solution again to remove unstable iron species. Finally, the product was filtered, washed and dried at 60 °C for 12 h.
Example 3:
Glucose (4 g) and melamine (2 g) were mixed in a 400 ml beaker. After stirring thoroughly, concentrated sulfuric acid (10 ml) was added to the mixture drop by drop. Then, the resulting mixture was placed into an autoclave at 120 °C for 10 h for primary carbonization. The product was then pumping filtered, washed and dried. Finally, the product was further carbonized at high temperature (600 °C) in nitrogen atmosphere for 2 h. Subsequently, the black powder was rinsed and dried at 60 °C for 12 h. The resulting black powder was labeled as carbonized beef. Subsequently, the product was ball-milled with FeCb solution. The mixture was heated at 800 °C for 2 h under N2 atmosphere. In order to remove unstable iron species, the obtained powder was immersed in 2 M HNO3 solution again to remove unstable iron species. Finally, the product was filtered, washed and dried at 60 °C for 12 h
Example 4:
To prepare carbonized silk, commercially available natural cocoons were first washed with warm deionized water and dried in an oven at 40 °C. The cocoons were then cut into 3-5 cm pieces and carbonized at 800 °C under N2 atmosphere for 2 h, and then ball-milled for 6 h. The resultant powder was immersed in 2 mol L 1 HNO3 for 48 h, washed with deionized water, dried in air. To prepare carbonized silk with N migration induced by Fe. The obtained product was mixed with the same quality of ferric chloride hexahydrate (FeCl3*6H2O), ball-milled for
6 h and heated for 2 h at 800 °C in a tube furnace under N2 atmosphere. The powder was then immersed in 2 mol L 1 HNO3 for 48 h, washed with deionized water and dried in air.
In this invention, a facile route to prepare Fe(lll)-treated N-doped carbon from nitrogen-rich biomass as sources of N and C is presented.
Claims
1 . A method for producing non-precious metal catalysts from N-rich biomass, which includes processing a precursor compound containing C, N, P, H and O elements by means of the following sequential steps:
(a) of drying and ball-milling;
(b) of heating at high temperature under inert gas atmosphere in a furnace to obtain carbonization;
(c) of treating in an acid to remove impurities;
(d) of treating with Fe species;
(e) of heating at high temperature in a nitrogen atmosphere to obtain calcination; and
(f) of treating in an acid to further remove impurities to a final carbon compound adapted to be non-precious metal catalyst.
2. A method as claimed in claim 1 , in which the precursor compound contains C, H, N, P and O biomass.
3. A method as claimed in claim 1 or claim 2, in which the precursor compound is derived from meat and bone.
4. A method as claimed in any one of the preceding claims, in which the acid is HNO3, H2SO4, HCI and/or H3PO4.
5. A method as claimed in any one of the preceding claims, in which the Fe species is FeC .
6. A method as claimed in any one of the preceding claims, in which step (b)
is conducted at a temperature of 300-1000 °C.
7. A method as claimed in any one of the preceding claims, in which step (e) is conducted at a temperature of 25-100 °C.
8. A method as claimed in any one of the preceding claims, in which in step (e) the N atoms in the precursor compounds are doped into the structure of the final carbon compound.
9. A method as claimed in any one of the preceding claims, in which step (e) results in FexN (x=0.5-3) compounds formed on the surface of the final carbon compound.
10. A method as claimed in any one of the preceding claims, in which the carbonized material of step (b) is used for oxygen reduction reaction.
1 1 . A non-precious metal catalyst material as produced by the method as claimed in any one of the preceding claims.
12. A non-precious metal catalyst as claimed in claim 1 1 , which is adapted to be used in fuel cells.
13. A method for producing al non-precious metal catalysts from N-rich biomass substantially as hereinbefore described with reference to any of the accompanying drawings.
14. A non-precious metal catalyst material substantially as hereinbefore described with reference to any of the accompanying drawings.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2676333A1 (en) * | 2009-08-21 | 2011-02-21 | Chunbao Xu | Peat derived carbon-based metal catalysts |
CN103007975A (en) * | 2012-12-04 | 2013-04-03 | 西北师范大学 | Preparation of nitrogen-containing carbon material and application thereof as oxygen-reduction electrocatalyst in fuel cell |
US8617768B2 (en) * | 2010-04-20 | 2013-12-31 | Nisshinbo Holdings Inc. | Carbon catalyst for direct fuel cell cathode, and direct fuel cell cathode and direct fuel cell using same |
-
2014
- 2014-08-17 WO PCT/IB2014/063945 patent/WO2016027123A1/en active Application Filing
-
2016
- 2016-02-29 ZA ZA2016/01389A patent/ZA201601389B/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2676333A1 (en) * | 2009-08-21 | 2011-02-21 | Chunbao Xu | Peat derived carbon-based metal catalysts |
US8617768B2 (en) * | 2010-04-20 | 2013-12-31 | Nisshinbo Holdings Inc. | Carbon catalyst for direct fuel cell cathode, and direct fuel cell cathode and direct fuel cell using same |
CN103007975A (en) * | 2012-12-04 | 2013-04-03 | 西北师范大学 | Preparation of nitrogen-containing carbon material and application thereof as oxygen-reduction electrocatalyst in fuel cell |
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