(19)
(11)EP 3 589 403 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
31.03.2021 Bulletin 2021/13

(21)Application number: 18760251.1

(22)Date of filing:  27.02.2018
(51)Int. Cl.: 
B01J 37/02  (2006.01)
H01M 4/86  (2006.01)
H01M 4/90  (2006.01)
B01J 27/24  (2006.01)
H01M 4/88  (2006.01)
H01M 8/16  (2006.01)
(86)International application number:
PCT/JP2018/007294
(87)International publication number:
WO 2018/159622 (07.09.2018 Gazette  2018/36)

(54)

PROCESS FOR PREPARING A SUPPORTED CATALYTIC MATERIAL, AND SUPPORTED CATALYTIC MATERIAL

VERFAHREN ZUR HERSTELLUNG EINES GETRÄGERTERN KATALYSATORMATERIALS UND GETRÄGERTES KATALYSATORMATERIAL

PROCÉDÉ DE PRÉPARATION D'UN MATÉRIAU CATALYTIQUE SUPPORTÉ ET MATÉRIAU CATALYTIQUE SUPPORTÉ


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 28.02.2017 US 201762464736 P

(43)Date of publication of application:
08.01.2020 Bulletin 2020/02

(73)Proprietor: Okinawa Institute of Science and Technology School Corporation
Kunigami-gun, Okinawa 904-0495 (JP)

(72)Inventors:
  • SCHAFFER-HARRIS Geoffrey Kellogg
    Kunigami-gun Okinawa 904-0495 (JP)
  • FEDOROVICH Viacheslav
    Kunigami-gun Okinawa 904-0495 (JP)
  • GORYANIN Igor
    Kunigami-gun Okinawa 904-0495 (JP)
  • SZYDLOWSKI Lukasz Michal
    Kunigami-gun Okinawa 904-0495 (JP)
  • SIMPSON David James Wilpault
    Kunigami-gun Okinawa 904-0495 (JP)
  • FILONENKO Georgy
    2613VG Delft (NL)

(74)Representative: Mewburn Ellis LLP 
Aurora Building Counterslip
Bristol BS1 6BX
Bristol BS1 6BX (GB)


(56)References cited: : 
WO-A1-2015/059718
CN-A- 105 932 309
US-A- 4 839 327
US-A1- 2014 036 201
US-A1- 2017 054 154
CN-A- 103 318 872
JP-A- 2006 289 326
US-A1- 2012 273 711
US-A1- 2015 086 727
  
  • YANG WENXIU, LIU XIANGJIAN, YUE XIAOYU, JIA JIANBO, GUO SHAOJUN: "Bamboo-like Carbon Nanotube/Fe 3 C Nanoparticle Hybrids and Their Highly Efficient Catalysis for Oxygen Reduction", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 137, no. 4, 4 February 2015 (2015-02-04), pages 1436-1439, XP0009518259, ISSN: 0002-7863, DOI: 10.1021/ja5129132
  
Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


Description

TECHNICAL FIELD



[0001] The present invention relates to a process for preparing a supported catalytic material, and a supported catalytic material.

BACKGROUND ART



[0002] Microbial fuel cells (MFCs) are devices, which converts chemical energy of compounds into electricity using microorganisms. Like a chemical fuel cells they contains anodic and cathodic zones separated in most cases by ion exchange membrane. The oxygen reduction reaction (ORR) is widely used cathodic reaction in fuel cells, which is enhanced by appropriate catalyst. Catalytic materials based on precious metals give the highest catalytic activity. However one of the limiting factors for commercialization of microbial fuel cells is the cost associated with precious metals.

[0003] In recent years, a variety of non-platinum catalysts for ORR have been identified and investigated. Among them cobalt or iron phthalocyanines are most investigated substances. These substances show comparable with platinum catalytic activity with respect to ORR. However such kind of catalysts is able to work in acid conditions only for the short time because of chemical reactions with acids. The heat treatment at high temperatures of these compounds was found as a way out from this situation. For example, heat treated iron(II) phthalocyanine can work in acids condition more than 1 year without loss of its activity. The well known non-platinum electrocatalysts are supported on high surface area of carbon materials. The heat treatment of metal-containing compounds together with nitrogen-containing compounds and carbon support makes possible the creation of special metal-nitrogen-carbon (M/N/C) complexes which possess catalytic activity with respect to ORR. At the moment there are several methods of fabrication of supported catalytic materials which use inexpensive precursors.

[0004] Regarding to a method of fabrication of supported catalytic material for ORR, Japanese Unexamined Patent Publication No. 2016-038988, WO 2014062639 A1 Japanese Unexamined Patent Publication No. 2014-196239, and Japanese Unexamined Patent Publication No. 2016-37404 are known. Patent Literature 5 describes a preparation method for carbon nanotubes. The preparation method comprises the following steps: firstly, mixing a catalyst with a complexing agent and a carbon source according to a proportion, and heating the mixture at 100-200 °C for 5-30 minutes; and then, dissolving the mixture in water, drying the mixture in an oven of 50-80 °C to obtain a jelly; and finally, heating the jelly under a protective gas condition to 400-1000 °C, and calcining the jelly for 30-120 minutes to obtain a final product. The carbon nanotubes disclosed are uniform in diameters, good in conductivity and good in catalytic properties and magnetic action. Patent Literature 6 describes a method of preparation of catalyst loaded carbon nanotubes which have ORR activity. The method uses urea, cyanamide or ethyl acetate as a carbon source.

CITATION LIST



[0005] 

Patent Literature 1: Japanese Unexamined Patent Publication No. 2016-038988

Patent Literature 2: WO 2014062639 A1

Patent Literature 3: Japanese Unexamined Patent Publication No. 2014-196239

Patent Literature 4: Japanese Unexamined Patent Publication No. 2016-37404

Patent Literature 5: CN 103 318 872

Patent Literature 6: Yang Wenxiu et al, J. of the American Chem. Soc., 137 (4), 1436-1439 (2015).


SUMMARY OF INVENTION


Technical Problem



[0006] However, an easier and lower-cost process for preparing a catalyst for the oxygen reduction reaction (ORR) is needed.

[0007] Hence, the present invention is intended to provide an easy and low-cost process for preparing a supported catalytic material used as a catalyst for the oxygen reduction reaction (ORR), for example, in a microbial fuel cell.

Solution to Problem



[0008] In order to achieve the above object, the present invention provides a process for preparing a supported catalytic material. The process comprises the step of: heating a precursor of support material impregnated with a mixture of chemical precursors. The mixture of chemical precursors includes a nitrogen-containing reducing reagent as a precursor and a transition metal-containing compound as a precursor. The process is characterised in that the precursor of the support material is a wood material.

[0009] The present invention also provides a supported catalytic material which prepared by the process of the present invention. The supported catalytic material has a surface comprising iron, nitrogen oxygen and carbon in following atomic percent content: Fe 0.23-11.22; C 43-94; O 4.7-42.68; N 0.2-2.78.

Advantageous Effects of Invention



[0010] According to the process of the present invention, a supported catalytic material can be prepared easily and at low-cost. The supported catalytic material, for example, can be used for a microbial fuel cell.

BRIEF DESCRIPTION OF DRAWINGS



[0011] 

Fig. 1 illustrates a graph regarding electrochemical comparison of catalytic properties of two types of supported catalytic materials for ORR. The solid line represents the supported catalytic material based on heat treated birch activated carbon and iron(II) phthalocyanine. The dashed line represents the supported catalytic material based on heat treated coconut shell charcoal, iron(III) nitrate and urea. Sweep rate 10mV/sec.

Fig. 2 illustrates a graph regarding optimization of catalytic properties of supported catalytic material based on heat treated coconut shell charcoal, iron(III) nitrate and urea by the variation of molar ratio iron/urea. The thin solid line represents the half voltammogram corresponding to the ratio iron/urea 1:7. The dashed line represents the half voltammogram corresponding to the ratio iron/urea 1:5. The bold solid line represents the half voltammogram corresponding to the ratio iron/urea 1:3. Sweep rate 10mV/sec.

[fig.3]Fig.3 illustrates half-voltammograms for comparison of the power generated by microbial fuel cell using different cathodic supported catalytic materials. The bold solid line represents the power generated by microbial fuel cell with supported catalytic material based on heat treated birch activated carbon and iron(II) phthalocyanine. The thin solid line represents the power generated by microbial fuel cell with supported catalytic material based on heat treated coconut shell charcoal, iron(III) nitrate and urea.

[fig.4]Fig.4 illustrates half-voltammograms for electrochemical catalytic activity for ORR when the precursor of supported material is pine wood. The bold solid line represents the half voltammogram corresponding to catalytic activity of heat treated pine wood material. The thin solid line represents the half voltammogram corresponding to catalytic activity of supported catalytic material based on heat treated pine wood, iron(III) nitrate and urea.

[fig.5A]Fig. 5A illustrates half-voltammograms of supported catalytic materials described in Example 5 obtained at different heat treatment temperatures measured in buffer with pH 4.5.

[fig.5B]Fig 5B illustrates a graph half-voltammograms of supported catalytic materials described in Example 5 obtained at different heat treatment temperatures measured in buffer with pH 8.

[fig.6]Fig 6 showsmagnetic susceptibility data for the sample described in Example 6.

[fig.7]Fig 7 illustrates half-voltammograms of supported catalytic materials described in Example 7 obtained at three different times of exposure at maximal heat treatment temperature.


Description of Embodiments



[0012] For the sake of clarity, in the present application, the term "catalytic material" is used to refer to compounds which result from pyrolysis of a mixture of chemical precursors but without support material. The term "supported catalyticmaterial" is any material which comprises a support material and a catalytic material on the surface and/or inside of the support material.

[0013] Terms used in the present specification each have a meaning commonly used in the art, unless otherwise stated.

[0014] In the process of the present invention, the nitrogen-containing reducing reagent compound is, for example, urea.

[0015] In the process of the present invention, the transition metal-containing compound is, for example, a transition metal salt.

[0016] In the process of the present invention, the transition metal salt is, for example, a salt from the group of nitrates, nitrites or their mixture.

[0017] In the process of the present invention, the transition metal salt, for example, contains iron or cobalt as a transition metal.

[0018] In the process of the present invention, the precursor of support material is, for example, a material that can be transferred into porous conductive material by pyrolysis.

[0019] In the process of the present invention, the precursor of support material is, for example, containing carbon as a major constituent.

[0020] In the process of the present invention, the precursor of support material is, for example, a wood material.

[0021] In the process of the present invention, the precursor of support material is, for example, a pine wood or a birch wood.

[0022] In the process of the present invention, the heating step is, for example, conducted at heating temperature 400-800 °C.

[0023] In the process of the present invention, the heating step is, for example, conducted at heating temperature 700 °C.

[0024] In the process of the present invention, the heating step is, for example, conducted during 1 hour.

[0025] In the process of the present invention, the process, for example, further comprises the step of: heating up from room temperature to the heating temperature before the heating step, wherein an atmosphere is self-generated during the heating up step.

[0026] In the process of the present invention, the heating up step is, for example, conducted during 1 hour.

[0027] In the process of the present invention, the atmosphere is, for example, self-generated at pressure 5-15 Pa at the temperature of 200-300 °C during 15 minutes.

[0028] In the process of the present invention, the supported catalytic material, for example, has better electrochemical catalytic activity at alkaline pH of the electrolyte.

[0029] In the process of the present invention, the supported catalytic material, for example, has magnetic properties facilitating the control of the concentration of supported catalytic material in space by means of an external magnetic field.

[0030] In the process of the present invention, the supported catalytic material is, used for a microbial fuel cell.

<Process for preparing a supported catalytic material>



[0031] As described above, the process of the present invention is a process for preparing a supported catalytic material. The process comprises the step of: heating a precursor of support material impregnated with a mixture of chemical precursors. The mixture of chemical precursors includes a nitrogen-containing reducing reagent as a precursor and a transition metal-containing compound as a precursor.

[0032] Accordingly, the process of the present invention contains the following steps: preparation of the solutions, which contain precursor compounds (mixture of chemical precursors); preparation of a precursor of support material; impregnation of the precursor of support material with the solution of precursor compounds; heat treatment of the mixture of the precursor compounds and the support material using specific temperature profile and variable atmosphere. Here, main criterion of the choice of materials and technological processes is, for example, low cost. By heat treatment of the mixture of the precursor compounds and the precursor of the support material, the supported catalytic material can be prepared.

[0033] In the process of the present invention, the process can use a wider class of chemical precursors and precursors of support materials, for example, simple and low-cost precursors, thus the process of the present invention can prepare a supported catalytic material easily and at low-cost.

[0034] The prepared supported catalytic material is, for example, a catalyst for the oxygen reduction reaction (ORR) as a cathodic reaction, preferably in a microbial fuel cell. Moreover, the supported catalytic material, for example, has better electrochemical catalytic activity at alkaline pH of the electrolyte, preferably at pH higher than 7, more preferably at pH of 8.

[0035] The prepared supported catalytic material, for example, has magnetic properties.

(transition metal-containing compound)



[0036] In the process of the present invention, a transition metal-containing compound is used as a chemical precursor. The transition metal-containing compound, for example, includes transition metal salt (transition metal-containing salt) hemoglobin, hemocyanin, or hemin, preferably, transition metal salt. The transition metal salt is not limited as long as it contains a transition metal from the collomn VIII of Mendeleev's table of elements. The transition metal, for example, includes iron, cobalt, nickel, platinum, palladium, iridium, ruthenium, rhodium or osmium. The transition metal salt is not particularly limited and may be a nitrate, nitride, nitrile or nitrite salt of transition metals from the collomn VIII of Mendeleev's table of elements, or their mixture. The transition metal salt may contain iron, cobalt, nickel, platinum, palladium, iridium, ruthenium, rhodium or osmium as a transition metal. Preferably, the transition metal salt is cobalt(III) salts or iron(III) salts, or their mixture.

(nitrogen-containing reducing reagent)



[0037] In the process of the present invention, a nitrogen-containing reducing reagent is used as a chemical precursor. The nitrogen-containing reducing reagent reduces metals which were in oxidized state (for example, Fe+3 into Fe+2). The nitrogen-containing reducing reagent may be used as long as they contain nitrogen and can reduce metals which were in oxidized state. Examples thereof include urea, imidazolidinyl urea (IMDZU) or diazolidinyl urea (DAZU).

[0038] Contrary to the substances described in other literatures, a class of the compounds (nitrogen-containing reducing reagents) is wider. Because of the simplest and inexpensive,urea is preferred.

(mixture of chemical precursors)



[0039] In the process of the present invention, a mixture of chemical precursors includes the nitrogen-containing reducing reagent as described above and the transition metal-containing compound (preferably, the transition metal salt) as described above. With the mixture of chemical precursors is impregnated a precursor of support material. The impregnation may be conducted by, for example, soaking the precursor of support material in the solution of the chemical precursors. The solution of the chemical precursors may be prepared by dissolving the chemical precursors in an appropriate solvent. The solvent may be water, alcohols, hydrocarbons and other organic solvents, preferably water. For example, the final solution of the chemical precursors (the mixture of chemical precursors)may beobtained just by adding deionized water of room temperature to dry components. Contrary to other literatures, no special mixing or drying of precursors is needed. This mixture may beintroduced into a precursor of support material by simply soaking the precursor of support material in the mixture.

[0040] The dry mixture of thesecompounds (the chemical precursors) maybe prepared with the appropriate molar ratio of a transition metal-containing compound to a nitrogen-containing reducing reagent. When a nitrogen-containing reducing reagent is urea, the molar ratio (transition metal-containing compound/urea) is, for example,within the range of 1:3 to 1:7; 1:3 to 1:5, preferably, equal to 1:5. This ratio (1:5) gives maximal catalytic activity.

(precursor of support material)



[0041] In the process of the present invention, a precursor of support material is impregnated with the mixture of chemical precursors and heated during the heating step. By heat treatment, the precursor of support material converts to a support material, which supports catalytic material on its surface and/or inside. As a precursor of support material,any material, which is able to soak the solution of above described chemical precursors and which is, for example, carbonized or which can be carbonized by means of heat treatment.

[0042] The class of materials whichis carbonized or can be carbonized is sufficiently wider than that, which claimed in other literatures. Among this class there are inexpensive materials with very low content of nitrogen such as cardboard or different types of wood. Traditional inexpensive materials like charcoals are applicable as precursors of support materials. For example, the precursor of support material may be a material which can be transferred into porous conductive material by pyrolysis. As the precursor of support material, all wooden materials, preferably pine wood or birch wood or coconut shell can be used. The carbonized materials may be also used as the precursor of support material. As the carbonized materials, different types of wooden charcoals can be used.

[0043] When the precursor of support material is a material which can be carbonized by means of heat treatment, carbonization may be conducted by the heat treatment of the heating step or may be conducted by another heat treatment before the heat treatment of the heating step. The precursor of support material is, preferably, pine or birch wood or coconut shell.

[0044] In the process of the present invention, a precursor of support material is impregnated with the mixture of chemical precursors before the heating step. The impregnation may be conducted by, for example, soaking the precursor of support material in the solution of chemical precursors. In the impregnation, the solution with the supported material may be stored, for example, at room temperature for 30 min.

(heating step)



[0045] In the heating step according to the process of the present invention, the precursor of support material impregnated with the mixture of chemical precursors is subjected to heat treatment (such as pyrolysis). The heat treatment procedure is, for example,carried out using specific temperature profile and variable anoxic atmosphere. The heat treatment procedure may be carried out under reduced pressure.

[0046] In some preferred embodiments, at the first stage, the linear increase of temperature up to the heating temperature may be applied during specific time, for example, 5 min to 3 hours, preferably 1 hour. The heating temperature is not particularly limited, may be within the range of 400 °C to 800 °C, preferably 700 °C. At the first stage, for example, at the temperature less than 200 °C the dehydration of precursor takes place. The pressure at this stage is, for example, 7 Pa. At the temperature of 400 °C, for example, the pressure inside the vacuum chamber increased up to 10 Pa and traces of ammonia weredetected. For example, contrary to other literatures,the necessary micro atmosphere of ammonia generates in porous of precursor of support material due to urea decomposition. For example, the atmosphere is self-generated at pressure 5-15 Pa at the temperature of 200-300 °C during 15 minutes. This first stage is also referred to as the heating up step.

[0047] In examples of the heat treatment, after the first stage, the maximum temperature may be maintained during specific time, for example, 5 min to 5 hours, preferably 1 hour. Then, the resulting product may be allowed to cool down to the room temperature, preferably, under reduced pressure. The cooling down procedure may take, for example, 4 to 8 hours, preferably 4 hours.

[0048] By the above heating step, the supported catalytic material is prepared. The prepared supported catalytic material has a catalytic activity. The prepared supported catalytic material, for example, has magnetic properties. Because of the magnetic properties, the supported catalytic material prepared by the process of the present invention facilitates the control of the concentration of supported catalytic material in space by means of an external magnetic field. To be more specific, by means of external magnet we can control the force of attachment of the granules of supported catalytic material. By variation of this force we can vary the local concentration of catalyst by means of the tightness of granules of supported catalytic material.

<supported catalytic material>



[0049] As described above, the supported catalytic material of the present invention is prepared by the process of the present invention. The supported catalytic material, for example, has a surface comprising iron, nitrogen oxygen and carbon in following atomic percent content: Fe 0.23-11.22; C 43-94; O 4.7-42.68; N 0.2-2.78.

[0050] As to the supported catalytic material of the present invention, for example, the above descriptions regarding the process of the present invention can be mentioned.

[0051] The present invention is described in detail below with reference to examples. It is to be noted, however, that the present invention is not limited thereto.

Examples



[0052] Equipment and instrumentation:
EYELA KDF-V50R vacuum furnace was used in all Examples. Coconut shell charcoal was supplied by Osaka Gas Chemicals (Japan). Remaining chemicals were supplied by Wako Pure Chemicals (Japan) and used without additional purification. Uniscan Instruments (UK) potentiostat was used for electrochemical characterization. Magnetic susceptibility was measured using Quantum Design (USA) DynaCool-9SR machine and XPS spectra were registered using Kratos Axis Ultra x-ray photoelectron spectrophotometer with mono (Al) x-ray source operating at anode voltage of 15 kV and emission current 10 mA (150 W). The catalyst surface was analyzed through a hybrid lens (700 um x 300 um analysis area). Data was processed using CasaXPS processing software (Tougaard background).

Example 1



[0053] In this experiment the catalytic activity of ORR was compared for two supported catalyticmaterials. For the first one, the birch activated carbon as a precursor of support material and iron(II) phthalocyanine as a chemical precursor were used (comparative example). For the second one the coconut shell charcoal as a precursor of support material and iron(III) nitrate and urea as chemical precursors were used (example).

[0054] The coconut shell charcoal and birch activated carbon were prepared in the following manner. Both charcoals were soaked in an excess of distilled water and drained to remove charcoal dust. Fresh distilled water was added in excess to the rinsed charcoals and the pH was adjusted (7.0) with concentrated hydrochloric acid. The charcoal suspensions were boiled for 1 hour, then it was allowed to cool and drained. The air-dried charcoals were heated under vacuum to 60 °C for 2 hours.

<Catalyst solutions>


(Iron-urea solution)



[0055] To 77 mL of distilled water was added 3.6 g (9 mmol) of iron(III) nitrate nona hydrate. The mixture was stirred to dissolve the iron(III) nitrate. To the resulting orange solution was added 4.8 g (80 mmol) of urea. The resulting solution was poured over 150 mL of vacuum-dried coconut shell charcoal in a 500-mL crucible (see above). The catalyst-charcoal mixture was stored at room temperature for 30 minutes.

(Iron(II) phthalocyanine solution)



[0056] To 100 mL of N-Methylpyrrolidone was added 5 g iron(II) phthalocyanine. The mixture was stirred to dissolve the iron(II) phthalocyanine. The resulting solution was poured over 150 mL of vacuum-dried birth activated carbon in a 500-mL crucible. The catalyst-charcoal mixture was stored at room temperature for 30 minutes. The concentration of iron was the same in both solutions.

<Pyrolysis>



[0057] The coconut shell charcoal saturated with the iron(III) nitrate and urea solution was heated in a vacuum furnace. The heat treatment procedure was carried out using special temperature profile and variable anoxic atmosphere. At the first stage the linear increase of temperature up to 700 °C was applied during one hour. At the first stage, at the temperature less than 200 °C the dehydration of precursor took place. The pressure at this stage was 7 Pa. At the temperature of 400 °C the pressure inside the vacuum chamber increased up to 10 Pa and traces of ammonia was detected in the out gases. After reaching the temperature of 700 °C then it was maintained during 1 hour.

[0058] The cooling down procedure from 700 °C to 200 °C took 4 hours in vacuum.

[0059] Then the final supported catalytic material was allowed to cool slowly under vacuum to room temperature.

[0060] The same temperature profile and anoxic atmosphere (7 Pa) were applied to mixture of birch activated carbon and the iron(II) phthalocyanine . However, no ammonia was detected in the out gases.

<Electrochemical analysis>



[0061] The comparison of catalytic properties of two types of supported catalytic materials for ORR was carried out using potentiostat and aerated three electrode electrochemical cell. The working electrode represented a perforated polymeric cylinder with a volume of 14 ml. The diameter of holes in the cylinder was less than average diameter of granules of supported catalytic material. The cylinder was filled with granules of supported catalytic material and tightly pressed by the upper lead, which had a metal electrical connector. Electrochemical tests were carried out in 0.1 M phosphate buffer solution at pH=4.5. The results of comparison are illustrated by Fig.1. Fig.1 contains half-voltammograms for both supported catalytic materials.

<Conclusion>



[0062] The catalytic activity which derived from the slopes of the curves is nearly two-fold higher for the precursors - iron(III) nitrate, urea and coconut shell charcoal rather than the reference catalyst based on iron(II) phthalocyanine and birch activated carbon. This point is additionally illustrated by a significantly higher current at the same negative potential.

Example 2



[0063] The influence of initial urea concentration on the final catalytic properties of the supported catalytic material was investigated.

[0064] The coconut shell charcoal was prepared in the same manner as in Example 1.

<Catalyst solutions>



[0065] Three solutions with chemical precursors were prepared:
  1. 1. A mixture of 17.0 g of iron(III) nitrate nonahydrate and 7.2 g of urea was dissolved in 77 mL of distilled water which resulting molar ratio iron/ urea 1:3.
  2. 2. A mixture of 17.0 g of iron(III) nitrate nonahydrate and 12.0 g of urea was dissolved in 77 mL of distilled water which resulting molar ratio iron/ urea 1:5.
  3. 3. A mixture of 17.0 g of iron(III) nitrate nonahydrate and 16.8 g of urea was dissolved in 77 mL of distilled water which resulting molar ratio iron/ urea 1:7.


[0066] Then resulting solutions was poured over 150 mL of vacuum-dried coconut shell charcoal in a 500-mL crucible. The catalyst-charcoal mixtures were stored at room temperature for 30 minutes.

<Pyrolysis>



[0067] Pyrolysis of three catalyst-charcoal mixtures was done in the same manner as in Example 1.

<Electrochemical analysis>



[0068] Electrochemical analyseswere carried out in the same electrochemical cell as in Example 1. The liquid phase (electrolyte solution) was represented by 0.1 M phosphate buffer solution at pH=8. The results of comparison are illustrated by Fig.2. Fig.2 contains half-voltammograms of each supported catalytic materials.

<Conclusion>



[0069] The catalytic activity which follows from the slops and intercepts of the curves is better for iron-urea molar ratio 1:5.

Example 3



[0070] Testing of the different types of supported catalytic materials in the working microbial fuel cell.

[0071] The microbial fuel cell for this test consisted of one anodic chamber inoculated with anaerobic sludge and two air breathing cathodic electrodes attached to both sides of anodic chamber. The volume of anodic chamber was 150 ml. Anodic and cathodic compartments were separated by ion exchange membrane. The supported catalytic material was attached to cathodic electrode, which serves as collector of electricity also. Two types of supported catalytic materials were used. Type 1 was attached to cathodic electrode on the left side of anodic zone, type 2 was attached to cathodic electrode on the right side of anodic zone.

[0072] For the first type the birch activated carbon as a precursor of support material and iron(II) phthalocyanine as a chemical precursor were used (comparative example). For the second type the coconut shell charcoal, iron(III) nitrate and urea were used as precursors (comparative example). Both supported catalytic materials were prepared using the same concentration and technology of manufacturing as in Example 1. The amount of supported catalytic materials of two types that was attached was the same and equal to 35 ml. The pH of cathodic electrolyte on both sides was 7.

[0073] Fig. 3 contains the power generated by both supported catalytic materials vs. current levels. The power values were calculated from polarization curves obtained by two electrode system where cathodic electrodes with different types of catalysts (supported catalytic materials) were used as working electrodes.

<Conclusion>



[0074] The coconut shell charcoal, iron(III) nitrate and urea as precursors for supported catalyst material generated more power than material based on birch activated carbon and iron(II) phthalocyanine.

Example 4



[0075] Electrochemical catalytic activity for ORR when the precursor of supported material is pine wood.

[0076] The iron-urea solution was prepared according to the following procedure. To 15 mL of distilled water was added 13.6 g (33.2 mmol) of iron nitrate nonahydrate. To the resulting solution was added 9.91 g (165 mmol) of urea. A 30-mL sample of 10-mm wooden pegs with diameter of 4 mm was saturated with the iron-urea solution by soaking for 16 hours. A separate 30-mL sample of 10-mm wooden pegs with diameter of 4 mm was saturated by soaking in distilled water. Each sample of saturated wooden pegs was pyrolyzed following the temperature profile described in Example 1. The resulting carbonized material was subjected to electrochemical tests. The electrochemical tests were carried out in the same three electrode cell as in Example 1 with pH of the solution equal to 7. The results are shown on Fig.4.

<Conclusion>



[0077] Wooden material can play the role of precursor of supporting material for final supported catalytic materials.

Example 5



[0078] The influence of maximal combustion temperature on the final catalytic properties of supported catalytic material was investigated.

[0079] The coconut shell charcoal was prepared in the same manner as in Example 1.

<Catalyst solutions>



[0080] Two solutions with catalysts precursors were prepared:
  1. 1. A mixture of 17.0 g of iron(III) nitrate nonahydrate and 7.2 g of urea was dissolved in 77 mL of distilled water which resulting molar ratio iron/ urea 1:3.
  2. 2. A mixture of 17.0 g of iron(III) nitrate nonahydrate and 9.6 g of urea was dissolved in 77 mL of distilled water which resulting molar ratio iron/ urea 1:4. Then resulting solutions was poured over 150 mL of vacuum-dried coconut shell charcoal in a 500-mL crucible. The catalyst-charcoal mixtures were stored at room temperature for 30 minutes.

<Pyrolysis>



[0081] The coconut shell charcoal saturated with the iron(III) nitrate and urea solutions with molar ratios iron/ urea 1:3 and molar ratio iron/ urea 1:4 was heated in a vacuum furnace under anoxic atmosphere. At the first stage the linear increase of temperature up to maximal temperature is applied during 1 hour. After reaching the maximal temperature, then it was maintained during 1 hour. The cooling down procedure from maximal temperature to 200 °C took 4 hours in vacuum. Then the final supported catalytic material was allowed to cool slowly under vacuum to room temperature. For each solution the applied maximal temperatures were: 400 °C, 500 °C, 600 °C, 700 °C, 800 °C.

[0082] The electrochemical tests of obtained supported catalytic materials at different temperatures were carried out in three electrode cell in the same manner as in Example 1. The buffer solutions that were used were 0.1 M phosphate buffers at pH 4.5 for iron/ urea 1:3 or pH 8 for iron/ urea 1:4. The results of comparison are illustrated by Figs.5A-B. Figs.5A-B contain half-voltammograms of each supported catalytic materials obtained at different maximal temperatures. The slope of the curves was used as a criterion to compare results because the bigger value of the slop the stronger the kinetics of electrode reaction and as a consequence the less polarizability of the whole cathodic electrode.

<Conclusion>



[0083] The catalytic activity which follows from the slops of the curves is better for the maximal temperatures within the range of 400 - 800 °C, the best for the maximal temperatures of 700 °C.

Example 6



[0084] Magnetic susceptibility for the catalyst prepared at 700 °C using the 1:5 iron-urea molar ratio (prepared in the same manner as in Example 1)was measured using a Quantum Design DynaCool-9SR physical properties measurement system (PPMS) equipped with a D525 vibrating sample magnetometer (VSM) module. The applied magnetic field varied from -2,000,000 A/m to +2,000,000 A/m at intervals of 50,000 A/m. The measurement temperature was maintained at 300 K. The powdered sample mass was 6.9 mg. The result is shown on Fig.6.

<Conclusion>



[0085] The results of the magnetic susceptibility measurements indicate that the magnetic remanence of the sample with no applied magnetic field is 4.69 x 10-6Am2 and the co-ercively or required field reversal after saturation for the sample is 49851 A/m.That clearly shows that the obtained material has pronounced magnetic properties.

Example 7



[0086] The choice of the optimal temperature profile of combustion for the creation of supported catalytic material.

[0087] In Example 5 it was shown that the maximal temperature of combustion 700 °C was optimal from point of view of half-voltammograms slopes, which characterizes the polarizability of the whole cathodic electrode. In present Example the time of exposure at maximal temperature was varied.

<Materials>



[0088] The coconut charcoal was prepared in the same manner as in Example 1.

[0089] A mixture of 17.0 g of iron(III) nitrate nonahydrate and 12.0 g of urea was dissolved in 77 mL of distilled water which resulted the molar ratio iron/ urea 1:5. This solution was used to saturate coconut shell charcoal.

<Temperature profile of combustion>



[0090] In all experiments, the first stage of the linear increase of temperature up to maximal temperature of 700 °C was the same. The duration of the first stage was 1 hour. After reaching the maximal temperature of 700 °C, this temperature was maintained during three different periods of times in three different experiments. These periods were: 3 hours, 1 hour, and 5 minutes. The cooling down procedure from maximal temperature to 200 °C took 4 hours and was the same in all experiments. Then the final supported catalytic material was allowed to cool slowly under vacuum to room temperature.

[0091] The electrochemical tests of obtained supported catalytic materials were carried out in three electrode cell in the same manner as in Example 1. The buffer solution that was used was 0.1 M phosphate buffers at pH 8. The results of comparison are illustrated by Fig.7. Fig.7 contains half-voltammograms of each supported catalytic materials obtained at three different times of exposure at maximal temperature. The criterion of comparison was the value of the slope of half-voltammograms.

<Conclusion>



[0092] The time of 1 hour is optimal time of exposure at maximal temperature for receiving supported catalytic material.

EXAMPLE 8



[0093] Comparison of the elemental composition of the surface of the samples prepared with different heat treatment temperatures and iron/urea loadings All samples were prepared according to procedure described in Example 1 and only Fe(NO3)3 and urea loadings were varied. Samples after heat treatment were used as solid unground blocks and measure using X-ray photoelectron spectroscopy to characterize the sample surface composition. The data is shown in Table 1. Instrument description provided in the Examples section.

[Table 1]



[0094] 
Table 1. Elemental composition of the materials surface at various pyrolysis temperatures and iron/urea loadings.
Loading Fe(NO3)39H2OLoading UreaT=400°CT=500°CT=600°CT=700°CT=800°C
10.1 g (0.025 mol) 6.0 g (0.1 mol) (iron: urea= 1:4) C: 43.57 % N: 2.53 % O: 42.68 % Fe: 11.22 % C: 60.51 % N: 2.26 % O: 29.60 % Fe: 7.64 % C: 74.85 % N: 1.31 % O: 18.83 % Fe: 5.01 % C: 75.16 % N: 1.47 % O: 19.00 % Fe: 4.38 % C: 92.71 % N: 0.30 % O: 5.75 % Fe: 1.24 %
13.4 g (0.033 mol) 6.0 g (0.1 mol) (iron: urea=1:3) C: 48.40 % N: 2.78 % O: 39.43 % Fe: 9.39 % C: 49.18 % N: 1.24 % O: 38.76 % Fe: 10.82 % C: 93.50 % N: 0.42 % O: 5.21 % Fe: 0.87 % C: 93.56 % N: 0.25 % O: 5.13 % Fe: 1.05 % C: 90.26 % N: 0.50 % O: 7.61 % Fe: 1.62 %
20.2 g (0.05 mol) 6.0 g (0.1 mol) (iron: urea=1:2) N/A N/A C: 67.07 % N: 1.94 % O: 24.64 % Fe: 6.36 % C: 63.50 % N: 0.31 % O: 27.98 % Fe: 8.21 % C: 93.89 % N: 0.22 % O: 4.77 % Fe: 1.12 %
Reference sample of support material not treated with either iron or urea
Coconut Shell Charcoal T=200°C C: 89.92 % N: 0.29 % O: 9.79 %        



Claims

1. A process for preparing a supported catalytic material, comprising the step of:
heating a precursor of a support material impregnated with a mixture of chemical precursors, wherein the mixture of chemical precursors includes:

a nitrogen-containing reducing reagent as a precursor, and

a transition metal-containing compound as a precursor,

characterised in that the precursor of the support material is a wood material.


 
2. The process of claim 1, wherein the nitrogen-containing reducing reagent compound is urea.
 
3. The process of claim 1 or 2, wherein the transition metal-containing compound is a transition metal salt, preferably a transition metal salt containing iron or cobalt as a transition metal.
 
4. The process of claim 3, wherein the transition metal salt is a salt from the group of nitrates, nitrites or their mixture.
 
5. The process of any one of claims 1 to 4, wherein the precursor of support material is a material that can be transformed into porous conductive material by pyrolysis, preferably containing carbon as a major constituent.
 
6. The process of claim 5, wherein the precursor of the support material is a pine wood or a birch wood.
 
7. The process of any one of claims 1 to 6, wherein the heating step is conducted at heating temperature 400-800 °C, preferably at 700 °C.
 
8. The process of claim 7, wherein the heating step is conducted during 1 hour.
 
9. The process of any one of claims 1 to 8, further comprising the step of:

heating up from room temperature to the heating temperature before the heating step, wherein

an atmosphere is self-generated during the heating up step.


 
10. The process of claim 9, the heating up step is conducted during 1 hour.
 
11. The process of claim 9 or 10, wherein the atmosphere is self-generated at pressure 5-15 Pa at the temperature of 200-300 °C during 15 minutes.
 
12. A supported catalytic material manufactured using the process of any one of claims 1 to 11, wherein the supported catalytic material has magnetic properties to facilitate the control of the concentration of supported catalytic material in space by means of an external magnetic field.
 
13. Use of a supported catalytic material manufactured using the process of any one of claims 1 to 11 as a microbial fuel cell.
 
14. A supported catalytic material manufactured using the process of any one of claims 1 to 11, wherein the supported catalytic material has a surface comprising iron, nitrogen oxygen and carbon in the following atomic percent content: Fe 0.23-11.22; C 43-94; O 4.7-42.68; N 0.2-2.78.
 


Ansprüche

1. Verfahren zur Herstellung eines geträgerten katalytischen Materials, das die folgenden Schritte umfasst:
das Erhitzen eines Vorläufers eines Trägermaterials, das mit einem Gemisch aus chemischen Vorläufern imprägniert ist, wobei das Gemisch aus chemischen Vorläufern Folgendes umfasst:

ein stickstoffhältiges Reduktionsregens als Vorläufer und

eine Übergangsmetall-hältige Verbindung als Vorläufer,
dadurch gekennzeichnet, dass der Vorläufer des Trägermaterials ein Holzmaterial ist.


 
2. Verfahren nach Anspruch 1, wobei die stickstoffhältige Reduktionsreagens-Verbindung Harnstoff ist.
 
3. Verfahren nach Anspruch 1 oder 2, wobei die Übergangsmetall-hältige Verbindung ein Übergangsmetallsalz ist, vorzugsweise ein Übergangsmetallsalz, das Eisen oder Kobalt als Übergangsmetall enthält.
 
4. Verfahren nach Anspruch 3, wobei das Übergangsmetallsalz ein Salz aus der Gruppe der Nitrate, Nitrite und Gemische davon ist.
 
5. Verfahren nach einem der Ansprüche 1 bis 4, wobei der Vorläufer des Trägermaterials ein Material ist, das mittels Pyrolyse zu porösem leitfähigem Material umsetzbar ist und das vorzugsweise Kohlenstoff als Hauptbestandteil enthält.
 
6. Verfahren nach Anspruch 5, wobei der Vorläufer des Trägermaterials Kiefernholz oder Birkenholz ist.
 
7. Verfahren nach einem der Ansprüche 1 bis 6, wobei der Heizschritt bei einer Heiztemperatur von 400 °C bis 800 °C, vorzugsweise bei 700 °C, durchgeführt wird.
 
8. Verfahren nach Anspruch 7, wobei der Heizschritt 1 Stunde lang durchgeführt wird.
 
9. Verfahren nach einem der Ansprüche 1 bis 8, das außerdem die folgenden Schritte umfasst:
das Aufheizen von Raumtemperatur auf die Heiztemperatur vor dem Heizschritt, wobei die Atmosphäre während des Aufheizschritts von selbst entsteht.
 
10. Verfahren nach Anspruch 9, wobei der Aufheizschritt 1 Stunde lang durchgeführt wird.
 
11. Verfahren nach Anspruch 9 oder 10, wobei die Atmosphäre bei einem Druck von 5 bis 15 Pa und einer Temperatur von 200 °C bis 300 °C über 15 Minuten von selbst entsteht.
 
12. Geträgertes katalytisches Material, das unter Anwendung eines Verfahrens nach einem der Ansprüche 1 bis 11 hergestellt ist, wobei das geträgerte katalytische Material über magnetische Eigenschaften verfügt, um die Steuerung der Konzentration des geträgerten katalytischen Materials im Raum mittels eines externen Magnetfelds zu erleichtern.
 
13. Verwendung eines geträgerten katalytischen Materials, das unter Anwendung eines Verfahrens nach einem der Ansprüche 1 bis 11 hergestellt wurde, als mikrobielle Brennstoffzelle.
 
14. Geträgertes katalytisches Material, das unter Anwendung eines Verfahrens nach einem der Ansprüche 1 bis 11 hergestellt ist, wobei das geträgerte katalytische Material eine Oberfläche aufweist, die Eisen, Stickstoff, Sauerstoff und Kohlenstoff in den folgenden Atomprozentgehalten umfasst: Fe 0,23-11,22; C 43-94; O 4,7-42,68; N 0,2-2,78.
 


Revendications

1. Procédé de préparation d'un matériau catalytique supporté, comprenant l'étape consistant à :
chauffer un précurseur d'un matériau de support imprégné d'un mélange de précurseurs chimiques, dans lequel le mélange de précurseurs chimiques comprend :

un réactif réducteur contenant de l'azote en tant que précurseur, et

un composé contenant un métal de transition en tant que précurseur,

caractérisé en ce que le précurseur du matériau de support est un matériau en bois.


 
2. Procédé selon la revendication 1, dans lequel le composé réactif réducteur contenant de l'azote est de l'urée.
 
3. Procédé selon la revendication 1 ou 2, dans lequel le composé contenant un métal de transition est un sel de métal de transition, de préférence un sel de métal de transition contenant du fer ou du cobalt en tant que métal de transition.
 
4. Procédé selon la revendication 3, dans lequel le sel de métal de transition est un sel du groupe des nitrates, des nitrites, ou de leur mélange.
 
5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel le précurseur de matériau de support est un matériau qui peut être transformé en matériau conducteur poreux par pyrolyse, contenant de préférence du carbone en tant que constituant majeur.
 
6. Procédé selon la revendication 5, dans lequel le précurseur du matériau de support est un bois de pin ou un bois de bouleau.
 
7. Procédé selon l'une quelconque des revendications 1 à 6, dans lequel l'étape de chauffage est effectuée à une température de chauffage de 400 à 800°C, de préférence à 700°C.
 
8. Procédé selon la revendication 7, dans lequel l'étape de chauffage est effectuée pendant 1 heure.
 
9. Procédé selon l'une quelconque des revendications 1 à 8, comprenant en outre l'étape consistant à :
Chauffer de la température ambiante à la température de chauffage avant l'étape de chauffage, dans lequel une atmosphère est auto-générée pendant l'étape de chauffage.
 
10. Procédé selon la revendication 9, dans lequel l'étape de chauffage est effectuée pendant 1 heure.
 
11. Procédé selon la revendication 9 ou 10, dans lequel l'atmosphère est auto-générée à une pression de 5 à 15 Pa à la température de 200 à 300°C pendant 15 minutes.
 
12. Matériau catalytique supporté fabriqué en utilisant le procédé de l'une quelconque des revendications 1 à 11, dans lequel le matériau catalytique supporté a des propriétés magnétiques pour faciliter la commande de la concentration de matériau catalytique supporté dans l'espace au moyen d'un champ magnétique externe.
 
13. Utilisation d'un matériau catalytique supporté fabriqué en utilisant le procédé de l'une quelconque des revendications 1 à 11 en tant que pile à combustible microbienne.
 
14. Matériau catalytique supporté fabriqué en utilisant le procédé selon l'une quelconque des revendications 1 à 11, dans lequel le matériau catalytique supporté a une surface comprenant du fer, de l'oxyde d'azote et du carbone en la teneur en pourcentage atomique suivante : Fe, 0,23 à 11,22 ; C, 43 à 94 ; O, 4,7 à 42,68 ; N, 0,2 à 2,78.
 




Drawing
























REFERENCES CITED IN THE DESCRIPTION



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Patent documents cited in the description




Non-patent literature cited in the description