SUPPORTED INTERMETALLIC COMPOUNDS AND USE AS CATALYST

Abstract

A composition comprising a ternary intermetallic compound X.sub.2YZ, wherein X, Y, and Z are different from one another; X being selected from the group consisting of Mn, Fe, Co, Ni, Cu, and Pd; Y being selected from the group consisting of Cr, Co, and Ni; and Z being selected from the group consisting of Al, Si, Ga, Ge, In, Sn, Zn, and Sb; wherein the ternary intermetallic compound is supported on a porous oxidic support material. The composition may be prepared by providing a liquid mixture of sources of X, Y, and Z, and the porous oxidic support material, removing the liquid and heating the resulting mixture in a reducing atmosphere. The composition is useful as catalyst.

Claims

1: A composition comprising a ternary intermetallic compound X.sub.2YZ, wherein X, Y, and Z are different from one another; X being selected from the group consisting of Mn, Fe, Co, Ni, Cu, and Pd; Y being selected from the group consisting of Cr, Co, and Ni; and Z being selected from the group consisting of Al, Si, Ga, Ge, In, Sn, Zn, and Sb; wherein the ternary intermetallic compound is supported on a porous oxidic support material.

2: The composition of claim 1, wherein the porous oxidic support material comprises one or more selected from the group consisting of: silica, alumina, titania, zirconia, and a mixed oxide of one or more selected from the group consisting of Si, Al, Ti, and Zr.

3: The composition of claim 1, wherein X or Y is Co, and wherein Z is selected from the group consisting of Al, Ga, In, and Zn.

4: The composition of claim 1, wherein the porous oxidic support material comprises a mixed oxide of Si and Al.

5: The composition of claim 1, wherein in the composition, the weight ratio of the ternary intermetallic compound relative to the porous oxidic compound is in the range of from 0.5:99.5 to 30:70.

6: The composition of claim 1, wherein Y is Ni, and wherein Z is Al, Si, Ga, In, Sn, or Sb.

7: The composition of claim 6, wherein the porous oxidic support material comprises silica.

8: The composition of claim 6, wherein in the composition, the weight ratio of the ternary intermetallic compound relative to the porous oxidic support is in the range of from 1:99.5 to 70:30.

9: The composition of claim 6, having a BET specific surface area in the range of from 150 to 400 m.sup.2/g.

10: The composition of claim 1, wherein at least 99 weight-% of the composition consists of the ternary intermetallic compound and the porous oxidic support material.

11: The composition of claim 1, wherein the intermetallic compound is a Heusler phase.

12: A process for preparing the composition of claim 1, comprising (i) preparing a liquid mixture comprising a source of X, a source of Y, a source of Z, and a source of the porous oxidic support material; (ii) removing the liquid phase from the mixture prepared in (i); and (iii) heating the mixture obtained from (ii) in a reducing atmosphere, thereby obtaining the intermetallic compound supported on the porous oxidic support material.

13: The process of claim 12, wherein the source of X is selected from the group consisting of salts of X, wherein the salts of X are selected from the group consisting of acetates, acetylacetonates, nitrates, nitrites, sulfates, hydrogensulfates, dihydrogensulfates, sulfites, hydrogensulfites, phosphates, hydrogenphosphates, dihydrogenphosphates, halides, cyanides, cyanates, isocyanates, and mixtures of two or more thereof; wherein the source of Y is selected from the group consisting of salts of Y, wherein the salts of Y are selected from the group consisting of acetates, acetylacetonates, nitrates, nitrites, sulfates, hydrogensulfates, dihydrogensulfates, sulfites, hydrogensulfites, phosphates, hydrogenphosphates, dihydrogenphosphates, halides, cyanides, cyanates, isocyanates, and mixtures of two or more thereof; wherein the source of Z is selected from the group consisting of salts of Z, wherein the salts of Z are selected from the group consisting of C1-C4 alkoxides, acetates, nitrates, nitrites, sulfates, hydrogensulfates, dihydrogensulfates, sulfites, hydrogensulfites, phosphates, hydrogenphosphates, dihydrogenphosphates, halides, cyanides, cyanates, isocyanates, and mixtures of two or more thereof; and wherein the source of the porous oxidic support material comprises one or more selected from the group consisting of silica, alumina, titania, zirconia, and a mixed oxide of one or more Si, Al, Ti, and Zr.

14: The process of claim 12, wherein (i) comprises (i.1) preparing a liquid mixture comprising a source of X, a source of Y, a source of Z, and a solvent; and (i.2) admixing the source of the porous oxidic support material with the mixture prepared in (i.1); wherein the solvent according to (i. 1) is a polar solvent; and wherein the solvent according to (i.2) is a polar solvent.

15: The process of claim 12, wherein removing the liquid phase from the mixture according to (ii) comprises heating the mixture prepared in (i).

16: The process of claim 12, wherein the reducing atmosphere according to (iii) comprises hydrogen.

17: The process of claim 12, further comprising (iv) cooling the intermetallic compound supported on the porous oxidic material, obtained from (iii).

18-19. (canceled)

Description

EXAMPLES

Reference Example 1.1: Determination of the Particle Size Via TEM

[0177] Samples for Transmission Electron Microscopy (TEM) were prepared on ultra-thin carbon TEM carriers. The powder was therefore dispersed in ethanol. One drop of the dispersion was applied between two glass objective slides and gently dispersed. The TEM carrier film was subsequently dipped on the resulting thin film. The samples were imaged by TEM using a Tecnai Osiris machine (FEI Company, Hillsboro, USA) operated at 200 keV under bright-field as well as high-angle annular dark-field scanning TEM (HAADF-STEM) conditions. Chemical composition maps were acquired by energy-dispersive x-ray spectroscopy (EDXS). Images and elemental maps were evaluated using the iTEM (Olympus, Tokyo, Japan, version: 5.2.3554) as well as the Esprit (Bruker, Billerica, USA, version 1.9) software packages. Particle size distributions were evaluated using the ParticleSizer plugin for FIJI.

Reference Example 1.2: X-Ray Powder Diffraction and Determination of the Crystallite Size

[0178] The X-ray powder diffraction (XRD) measurements were carried out with a D 5005 type diffractometer of Siemens/Bruker AXS using a Cu Kalpha Source (lambda=0.15405 nm). The source was operated at 35 kV and 25 mA and the data were collected in a 2theta range from 3 to 110 with a step size of 0.1 (2theta). The crystallite sizes were determined by the Scherer equation using peaks at 79 2theta. A Gaussian fit was used to determine the full width at half maximum (FWHM).

Reference Example 1.3: Determination of the BET Specific Surface Area, the Total Pore Volume and the Average Pore Size

[0179] The BET specific surface area was determined according to DIN 66131 via nitrogen adsorption/desorption at a temperature of 77 K. The total pore volume was determined via mercury intrusion porosimetry according to DIN 66133. The average pore size was determined via mercury intrusion porosimetry according to DIN 66133.

Reference Example 1.4: Starting Materials

[0180] 1.4.1 Metal Sources

[0181] The following materials were employed for preparing the intermetallic compounds (see Table 1 below):

TABLE-US-00001 TABLE 1 Starting materials molecular weight/ precursor formula (g/mol) chromium(III) nitrate nonahydrate Cr(NO.sub.3).sub.39 H.sub.2O 400.15 cobalt(II) nitrate hexahydrate Co(NO.sub.3).sub.26 H.sub.2O 291.04 gallium(III) nitrate 5.5hydrate Ga(NO.sub.3).sub.35.5 H.sub.2O 354.82 aluminum nitrate nonahydrate Al(NO.sub.3).sub.39 H.sub.2O 375.13 zinc nitrate tetrahydrate Zn(NO.sub.3).sub.24 H.sub.2O 261.45 indium(III) nitrate dihydrate In(NO.sub.3).sub.32 H.sub.2O 336.86 copper(II) nitrate pentahemihydrate Cu(NO.sub.3).sub.22.5 H.sub.2O 232.59 antimony(III) acetate (CH.sub.3CO.sub.2).sub.3Sb 298.89 tin(II) chloride dihydrate SnCl.sub.22 H.sub.2O 225.64 nickel(II) nitrate hexahydrate Ni(NO.sub.3).sub.26 H.sub.2O 290.80

[0182] 1.4.2 Porous Oxidic Materials [0183] a) Silica: As porous oxidic support material, fumed silica according to the following specification was employed: Sigma Aldrich, lot no. S5130 (particle size=0.007 micrometer, BET specific surface area=370-420 m.sup.2/g, density=2.3 lb/ft.sup.3 (1 lb/ft.sup.2=16.018463 kg/m.sup.3)). [0184] b) Zeolite: As a further oxidic support material, a zeolite ZSM-5 (framework type MFI) was employed. The zeolitic material was prepared as follows: a solution consisting of 12.72 g sulfuric acid and 1.8 g sodium aluminate in 240 g water was produced. Under stirring 160 g sodium silicate solution was slowly added. Once a homogenous synthesis gel has formed a solution of 19.2 g tetrapropylammonium bromide and 32 g water were slowly added. The synthesis gel was stirred at room temperature for 0.5 h. Afterwards the crystallization was carried out in a rotating stainless steel autoclave (50 rpm) with a Teflon inlay at 180 C. for 72 h. The BET specific surface area was 452 m.sup.2/g. The X-Ray diffraction pattern of the ZSM-5 zeolitic material is shown in FIG. 39 for 2theta in the range of from 3 to 50. An SEM image is shown in FIG. 40. The respectively prepared zeolite ZSM-5 had a molar ratio of SiO.sub.2:Al.sub.2O.sub.3=61.

Example 1: Preparation of Ternary Intermetallic Compounds Supported on a Porous Oxidic Support

[0185] According to Example 1, the following ternary intermetallic compounds supported on a porous oxidic support were prepared (see Table 2 below). In Example 1.1, the typical process is disclosed.

TABLE-US-00002 TABLE 2 Compositions prepared according to Example 1 metal mass mass X mass Y mass Z composition content/ support/ amount precursor/ amount precursor/ amount precursor/ X Y Z support wt.-% g X/mmol g Y/mmol g Z/mmol g Co Cr Al ZSM-5 5 2.15 1.15 0.33 0.57 0.23 0.58 0.22 Co Cr Ga ZSM-5 5 2.22 0.98 0.28 0.49 0.20 0.49 0.17 Co Cr In ZSM-5 5 2.19 0.81 0.24 0.41 0.16 0.41 0.14 Co Cr Zn ZSM-5 5 2.17 0.97 0.28 0.49 0.19 0.49 0.13 Cu Co Al ZSM-5 5 2.33 1.15 0.27 0.58 0.17 0.58 0.22 Cu Co Ga ZSM-5 5 2.11 0.87 0.20 0.43 0.13 0.43 0.15 Cu Co In ZSM-5 5 2.10 0.47 0.11 0.47 0.14 0.47 0.16 Cu Co Zn ZSM-5 5 2.23 0.94 0.22 0.47 0.14 0.47 0.12

Example 1.1: Preparation of 5 Weight-% Co.SUB.2.CrAl Supported on Zeolite ZSM-5

[0186] Co(NO.sub.3).sub.2.6H.sub.2O (1.57 g, 5.39 mmol), Cr(NO.sub.3).sub.3.9H.sub.2O (1.08 g, 2.69 mmol) and Al(NO.sub.3).sub.3.9H.sub.2O (1.01 g, 2.69 mmol) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 minutes. ZSM-5 (2.15 g) and 100 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40 C. The residue was dried at 110 C. for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 minutes at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at 900 C. The maximum temperature was achieved by heating rate of 10 K/min.sup.1 and kept constant for 8 h. Finally, the samples were cooled to room temperature. The crystal structure of the prepared ternary intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co.sub.2CrAl/ZSM-5 for the range 2theta=3-100 is shown in FIG. 1. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.2: Preparation of 5 Weight-% Co.SUB.2.CrGa Supported on Zeolite ZSM-5

[0187] The preparation was carried out analogously to Example 1.1.

[0188] The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co.sub.2CrGa/ZSM-5 for the range 2theta=3-100 is shown in FIG. 2. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.3: Preparation of 5 Weight-% Co.SUB.2.CrIn Supported on Zeolite ZSM-5

[0189] The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co.sub.2CrIn/ZSM-5 for the range 2theta=3-100 is shown in FIG. 3. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.4: Preparation of 5 Weight-% Co.SUB.2.CrZn Supported on Zeolite ZSM-5

[0190] The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Co.sub.2CrZn/ZSM-5 for the range 2theta=3-100 is shown in FIG. 4. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.5: Preparation of 5 Weight-% Cu.SUB.2.CoAl Supported on Zeolite ZSM-5

[0191] The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Cu.sub.2CoAl/ZSM-5 for the range 2theta=3-100 is shown in FIG. 5. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.6: Preparation of 5 Weight-% Cu.SUB.2.CoGa Supported on Zeolite ZSM-5

[0192] The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 wt.-% Cu.sub.2CoGa/ZSM-5 for the range 2theta=3-100 is shown in FIG. 6. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.7: Preparation of 5 Weight-% Cu.SUB.2.CoIn Supported on Zeolite ZSM-5

[0193] The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 wt.-% Cu.sub.2CoIn/ZSM-5 for the range 2theta=3-100 is shown in FIG. 7. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta=3-40 can be assigned to the ZSM-5 support.

Example 1.8: Preparation of 5 Weight-% Cu.SUB.2.CoZn Supported on Zeolite ZSM-5

[0194] The preparation was carried out analogously to Example 1.1. The crystal structure of the intermetallic compounds was investigated by X-ray powder diffraction. The X-ray diffraction pattern of 5 weight-% Cu.sub.2CoZn/ZSM-5 for the range 2theta=3-100 is shown in FIG. 8. The sharp reflections between 2theta=40-100 are caused by crystalline nanoparticles. The diffraction peaks between 2theta 3-40 can be assigned to the ZSM-5 support.

Example 2: Preparation of Ternary Intermetallic Compounds Supported on a Porous Oxidic Support

Example 2.1: Preparation of 30 Weight-% Cu.SUB.2.NiZ Supported on SiO.SUB.2

[0195] All combinations prepared by the procedure as described in Example 2.1.1 below were prepared with a total metal content of 30 weight-% and a metal stoichiometry of X:Y:Z=2:1:1.

Example 2.1.1: Preparation of 30 Weight-% Cu.SUB.2.NiAl Supported on SiO.SUB.2

[0196] Cu(NO.sub.3).sub.2.2.5H.sub.2O (1.96 g, 8.44 mmol), Ni(NO.sub.3).sub.2.6H.sub.2O (1.23 g, 4.22 mmol) and SnCl.sub.2.2H.sub.2O (0.95 g, 4.22 mmol) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 min. Fumed silica (3.00 g, 7 nm) and 10 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40 C. The residue was dried at 110 C. for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 min at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at 880 C. The detailed temperature program for the reducing method is given in Table 3 below. Finally, the samples were cooled to room temperature.

TABLE-US-00003 TABLE 3 Temperature program for the reduction according to Example 2.1.1 temperature ramp/(K/min) Temperature/ C. Holding temperature for . . . min 25 5 100 0.5 210 60 5 880 180

[0197] The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiAl/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 9. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.1.2: Preparation of 30 Weight-% Cu.SUB.2.NiGa Supported on SiO.SUB.2

[0198] The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiGa/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 10. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.1.3: Preparation of 30 Weight-% Cu.SUB.2.NiIn Supported on SiO.SUB.2

[0199] The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiIn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 11. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.1.4: Preparation of 30 Weight-% Cu.SUB.2.NiSb Supported on SiO.SUB.2

[0200] The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSbISiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 12. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.1.5: Preparation of 30 Weight-% Cu.SUB.2.NiSi Supported on SiO.SUB.2

[0201] The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern of 30 weight-% Cu.sub.2NiSi/SiO.sub.2 for the range 2theta=15-100 is shown in FIG. 13. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.1.6: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2

[0202] The preparation was carried out analogously to Example 2.1.1. The crystal structure of the intermetallic compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern of 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the range 2theta=15-100 is shown in FIG. 14. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. TEM images (see FIG. 29) of show particles in the range from a few nanometer up to 400 nm. The particles containing Cu/Ni/Sn are of spherical shape.

Example 2.2: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at Different Reduction Temperatures

[0203] All combinations prepared by the procedure as described in Example 2.2 were prepared with a total metal content of 30 weight-% and a metal stoichiometry of X:Y:Z=2:1:1 and varying reduction temperatures.

[0204] Cu(NO.sub.3).sub.2.2.5H.sub.2O (1.96 g, 8.44 mmol) Ni(NO.sub.3).sub.2.6H.sub.2O (1.23 g, 4.22 mmol) and SnCl.sub.2.2H.sub.2O (0.95 g, 4.22 mmol) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 min. Fumed silica (3.00 g, 7 nm) and 10 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40 C. The residue was dried at room temperature for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 min at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at the respective temperature indicated in the Examples 2.2.1 to 2.2.6. The maximum temperature was achieved using a heating rate of 10 K/min and kept constant for 3 h. Finally, the samples were cooled to room temperature.

Example 2.2.1: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at a Maximum Temperature of 500 C.

[0205] The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 15. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The broad diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the Heusler L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9.

Example 2.2.2: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at a Maximum Temperature of 600 C.

[0206] The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 16. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The broad diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the Heusler L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9.

Example 2.2.3: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at a Maximum Temperature of 700 C.

[0207] The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 17. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The broad diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the Heusler L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9.

Example 2.2.4: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at a Maximum Temperature of 800 C.

[0208] The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 18. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The broad diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the Heusler L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9.

Example 2.2.5: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at a Maximum Temperature of 900 C.

[0209] The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 19. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The broad diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the Heusler L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9. It is observed that heating above 800 C. avoids phase impurities.

Example 2.2.6: Preparation of 30 Weight-% Cu.SUB.2.NiSn Supported on SiO.SUB.2 .at a Maximum Temperature of 1000 C.

[0210] The crystal structure of the Heusler compounds was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 20. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The broad diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the Heusler L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9. It is observed that heating above 800 C. avoids phase impurities.

Example 2.3: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with Different Metal Content

[0211] All combinations prepared by the procedure as described in Example 2.3 were prepared with a metal stoichiometry of X:Y:Z=2:1:1 and varying metal content, as shown in Table 4 below:

TABLE-US-00004 Table 4 Compositions prepared according to Example 2.3 metal mass X mass Y mass Z composition content/ Example amount precursor/ amount precursor/ amount precursor/ X Y Z support wt.-% # X/mmol g Y/mmol g Z/mmol g Cu Ni Sn SiO.sub.2 30 2.3.1 8.44 1.96 4.22 1.23 4.22 0.95 Cu Ni Sn SiO.sub.2 20 2.3.2 4.93 1.15 2.46 0.72 2.46 0.56 Cu Ni Sn SiO.sub.2 15 2.3.3 3.48 0.81 1.74 0.51 1.74 0.39 Cu Ni Sn SiO.sub.2 10 2.3.4 2.19 0.51 1.09 0.32 1.09 0.25 Cu Ni Sn SiO.sub.2 5 2.3.5 1.04 0.24 0.52 0.15 0.52 0.12 Cu Ni Sn SiO.sub.2 2 2.3.6 0.40 0.09 0.20 0.06 0.20 0.05 Cu Ni Sn SiO.sub.2 1 2.3.7 0.20 0.05 0.10 0.03 0.10 0.02

[0212] The compositions were prepared as follows: Cu(NO.sub.3).sub.2.2.5H.sub.2O (respective amount according to Table 4) Ni(NO.sub.3).sub.2.6H.sub.2O (respective amount according to Table 4) and SnCl.sub.2.2H.sub.2O (respective amount according to Table 4) were dissolved in 80 ml methanol. A round bottom flask containing the solution was placed in an ultrasonic bath and treated for 30 min. Fumed silica (3.00 g, 7 nm) and 10 ml methanol were supplied to another round bottom flask and sonicated for 30 min. The precursor solution was added to the fumed silica suspension and sonicated for 30 min at room temperature. Then, the methanol was removed in a rotary evaporator with the water bath temperature adjusted to 40 C. The residue was dried at room temperature for 18 h. The solid was grounded to a powder and filled into a vertically arranged flow-type quartz reactor. The reactor was thoroughly purged with nitrogen (100 ml/min) for 10 min at room temperature. The powder was then reduced in a mixture of flowing hydrogen and nitrogen (100 ml/min hydrogen and 100 ml/min nitrogen) at 800 C. The maximum temperature was achieved at a heating rate of 10 K/min and kept constant for 3 h. Finally, the samples were cooled to room temperature. The L2.sub.1 structure cannot be undoubtedly verified for metal content below 10 wt.-%. The signal broadening is assumed to be resulting from decreasing the crystallite sizes. In FIG. 28, the crystallite size is shown as a function of the metal content of the Heusler compounds of Examples 2.3.1 to 2.3.4.

Example 2.3.1: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 30 Weight-%

[0213] The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 30 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 21. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the L2.sub.1 phase are observed at 25.9, 30 42.9, 62.4 and 78.9. In contrast to Example 2.1.6, TEM (see FIG. 30) show larger particles with a size of up to 2 micrometer. The two-phased janus particles contain Cu/Ni/Sn.

[0214] The particle size distribution of the Heusler compound, determined according to reference example 1.1, afforded a D10 value of about 47 nm, a D50 value of about 68 nm, and a D90 value of about 129 nm (see FIG. 41).

Example 2.3.2: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 20 Weight-%

[0215] The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 20 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 22. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the L2.sub.1 phase are observed at 25.9, 30 42.9, 62.4 and 78.9.

Example 2.3.3: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 15 Weight-%

[0216] The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 15 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 23. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9.

Example 2.3.4: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 10 Weight-&

[0217] The crystal structure of the Heusler compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 10 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 24. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica. The characteristic signals for the L2.sub.1 phase are observed at 25.9, 30, 42.9, 62.4 and 78.9. TEM (see FIG. 31) show nano-particles in a range from 2 to 50 nm. The particles are homogeneously distributed on the support. Like in Example 2.3.1, some of the particles show janus shape.

[0218] The particle size distribution of the Heusler compound, determined according to reference example 1.1, afforded a D10 value of about 5 nm, a D50 value of about 7 nm, and a D90 value of about 13 nm (see FIG. 41).

Example 2.3.5: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 5 Weight-%

[0219] The crystal structure of the intermetallic compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 5 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 25. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.3.6: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 2 Weight-%

[0220] The crystal structure of the intermetallic compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 2 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 26. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 2.3.7: Preparation of Cu.SUB.2.NiSn Supported on SiO.SUB.2 .with a Metal Content of 1 Weight-%

[0221] The crystal structure of the intermetallic compound was examined by X-ray powder diffraction. The X-ray diffraction pattern for 1 weight-% Cu.sub.2NiSn/SiO.sub.2 for the angle range 2theta=15-100 is shown in FIG. 27. The sharp reflections between 2theta=20-100 are caused by crystalline nanoparticles. The wide diffraction peak between 2theta=20-35 can be assigned to the support fumed silica.

Example 3: Testing of the Supported Ternary Intermetallic Compounds of Example 1 as Catalytically Active MaterialsOxidation of Cyclohexane

[0222] The catalytic activities of the intermetallic compounds supported on ZSM-5 prepared according to Examples 1.1 to 1.4 (Co.sub.2CrAl/ZSM-5, Co.sub.2CrGa/ZSM-5, Co.sub.2CrIn/ZSM-5, Co.sub.2CrZn/ZSM-5) and Examples 1.5 to 1.8 (Cu.sub.2CoAl/ZSM-5, Cu.sub.2CoGa/ZSM-5, Cu.sub.2CoIn/ZSM-5, Cu.sub.2CoZn/ZSM-5) were tested in the oxidation of cyclohexane with molecular oxygen.

[0223] The oxidation of cyclohexane was carried out in a stainless steel autoclave with Teflon inlay, which was filled with 25 ml cyclohexane, 50 ml acetone as solvent and 250 mg of the supported intermetallic compound. Then the autoclave was pressurized with 2 MPa of synthetic air (20.5% O.sub.2 in N.sub.2) and heated up. After the reaction temperature of 150 C. was reached the reaction was carried out under stirring for 6 h. Product samples were analyzed in a gas chromatograph (HP 6890 Series) with integrated mass selective detector (HP 5973). For this purpose, 10 microL of the samples were mixed with 2 microL toluene (external standard) and diluted in 1000 microL acetone. The conditions for the gas chromatographic analysis of the products from the cyclohexane oxidation were chosen as follows:

[0224] sample volume: 4 microL

[0225] injector temperature: 200 C.

[0226] heating rate: start at 35 C., 10 min isothermal, heating rate 30 K/min to 200 C.

[0227] eluent: He

[0228] flow rate: 139.3 ml/min

[0229] column head pressure: 1.2 bar (abs)

[0230] split ratio: 50:1

[0231] column: CP-SIL 5 CB, 100% dimethylpolysiloxane [0232] length=25 m, film thickness=0.25 micrometer

[0233] detector: MS

[0234] As products, cyclohexanone (CHO) and cyclohexanol (CHOL) were identified.

[0235] The yields of cyclohexanone and cyclohexanole obtained when using the intermetallic compounds of Examples 1.1 to 1.4 (Co.sub.2CrAl/ZSM-5, Co.sub.2CrGa/ZSM-5, Co.sub.2CrIn/ZSM-5, Co.sub.2CrZn/ZSM-5) are shown in FIG. 32, plotted versus the reaction time. In the reference reaction over ZSM-5, only a low yield was observed. For the ZSM-5-supported intermetallic compounds an increase in activity in comparison to the ZSM-5-type zeolite could be detected. The highest yield was found for Co.sub.2CrAl/ZSM-5.

[0236] The yields of cyclohexanone and cyclohexanole obtained when using the intermetallic compounds of Examples 1.5 to 1.8 (Cu.sub.2CoAl/ZSM-5, Cu.sub.2CoGa/ZSM-5, Cu.sub.2CoIn/ZSM-5, Cu.sub.2CoZn/ZSM-5) are shown in FIG. 33, plotted versus the reaction time. In the reference reaction over zeolite ZSM-5, only a low yield was observed. Except for the Cu.sub.2CoIn/ZSM-5 material the ZSM-5 supported intermetallic compounds showed an increase in activity in comparison to ZSM-5. The highest yield for both products was found for Cu.sub.2CoZn/ZSM-5.

[0237] An overview of the results of the cyclohexane oxidation is shown in FIG. 34.

Example 4: Testing of the Supported Ternary Intermetallic Compounds of Example 2 as Catalytically Active Materials

Example 4.1 Hydrogenation of Cinnamaldehyde ((2E)-3-Phenylprop-2-Enal)

[0238] The catalytic activities of the synthesized supported intermetallic compounds were tested in the cinnamaldehyde hydrogenation reaction. In particular, the compounds of Examples 2.1.6 (30 weight-% Cu.sub.2NiSn/SiO.sub.2), Example 2.3.1 (30 weight-% Cu.sub.2NiSn/SiO.sub.2) and Example 2.3.4 (10 weight-% Cu.sub.2NiSn/SiO.sub.2) were tested.

[0239] A batch autoclave with magnetic stirring was supplied with 150 ml cyclohexane, 5 ml cinnamaldehyde, 1 ml tetradecane as internal standard and 0.5 g of the respective supported intermetallic compound. The autoclave was sealed and afterwards flushed 3 with 7 bar of nitrogen. After 3 times flushing with 20 bar(abs) hydrogen, the reactor was heated up to 150 C. By reaching 150 C., hydrogen was used to set the pressure to 50 bar(abs), which was defined as the start time of the reaction. At regular time intervals, the reaction mixture was analyzed by gas chromatography. The conditions for the gas chromatographic analysis of the products from the hydrogenation of cinnamaldehyde were chosen as follows:

[0240] stationary phase: CP-SIL 5 CB

[0241] length: 25 m

[0242] inner diameter: 250 micrometer

[0243] film thickness: 0.25 micrometer

[0244] oven temperature: start: 120 C. 1 min [0245] 7 K/min 160 C. [0246] 50 K/min 220 C. 3 min

[0247] inlet temperature: 220 C.

[0248] split ratio: 30:1

[0249] total flow rate: 32.6 ml/min

[0250] eluent: N.sub.2

[0251] velocity: 30 cm/s

[0252] detector: flame ionization detector

[0253] makeup flow: 45 ml/min

[0254] hydrogen flow: 40 ml/min

[0255] air flow: 450 ml/min

[0256] In FIG. 35, the catalytic conversion of cinnamaldehyde as a function of the reaction time is shown. Clearly, all tested catalysts are active in the hydrogenation of cinnamaldehyde.

[0257] In FIG. 36, the selectivities of these catalysts with respect to hydrocinnamaldehyde (HZAH), cinnamyl alcohol (ZAO) and hydrocinnamyl alcohol (HZAO) at a conversion of 5% are shown. It is noted that all catalysts show similar selectivities.

[0258] In FIG. 37, the selectivities of these catalysts with respect to hydrocinnamaldehyde (HZAH), cinnamyl alcohol (ZAO) and hydrocinnamyl alcohol (HZAO) after a reaction time of 300 min are shown. The respectively observed conversions after 300 min correlate with the findings from the TEM characterization: the largest particles have the smallest active surface and therefore the lowest conversion.

Example 4.2 Dehydrogenation of Propane

[0259] The catalytic activities of the synthesized supported intermetallic compound of Example 2.1.6 (30 weight-% Cu.sub.2NiSn/SiO.sub.2) was tested in the dehydrogenation of propane. The time-on-stream experiment was carried out in a fixed-bed flow-type reactor at 650 C. The catalyst particle size was set to 255-355 micrometer by grounding and sieving. 250 mg of catalyst were tested in a mixture of flowing propane (3 ml/min) and nitrogen (27 ml/min) at atmospheric pressure. At regular time intervals, the product mixture was analyzed by gas chromatography. The conditions for the gas chromatographic analysis of the products from the dehydrogenation of propane were chosen as follows:

[0260] stationary phase: HP-Plot

[0261] length: 50 m

[0262] inner diameter: 530 micrometer

[0263] film thickness: 0.15 micrometer

[0264] oven temperature: 120 C.

[0265] inlet temperature: 200 C.

[0266] split ratio: 10:1

[0267] total flow rate: 81.6 ml/min

[0268] eluent: N.sub.2

[0269] velocity: 56 cm/s

[0270] detector: flame ionization detector

[0271] makeup flow: 45 ml/min

[0272] hydrogen flow: 40 ml/min

[0273] air flow: 450 ml/min

[0274] It was found that after a reaction time of 21 h, the tested supported intermetallic compound shows a conversion of 42%, a selectivity with respect to propene of 40%, a selectivity with respect to ethene of 37.5%, a selectivity with respect to ethane of 2%, and a selectivity with respect to methane of 20.5%

Example 4.3 Knoevenagel Condensation Reaction

[0275] The catalytic activities of the synthesized supported intermetallic compound of Examples 2.1.1 to 2.1.6 (30 weight-% Cu.sub.2NiZ/SiO.sub.2) were tested in the Knoevenagel condensation reaction.

[0276] Malononitrile (0.52 g, 8 mmol), benzaldehyde (0.84 g, 8 mmol), 20 ml toluene as a solvent and 0.2 g of 1,4-dichlorbenzene as internal standard were mixed in a 50 ml two-necked flask equipped with a reflux condenser. The mixture was heated in an oil bath and 0.4 g of the respective supported intermetallic compound were added when the maximum temperature of 80 C. was reached. At regular time intervals, the reaction mixture was analyzed by gas chromatography. The conditions for the gas chromatographic analysis of the products from the hydrogenation of cinnamaldehyde were chosen as follows:

[0277] stationary phase: CP-SIL 5 CB

[0278] length: 25 m

[0279] inner diameter: 250 micrometer

[0280] film thickness: 0.25 micrometer

[0281] oven temperature: start: 55 C. 1 min [0282] 40 K/min 250 C. 3 min

[0283] inlet temperature: 245 C.

[0284] split ratio: 50:1

[0285] total flow rate: 53.3 ml/min

[0286] eluent: He

[0287] velocity: 40 cm/s

[0288] detector: mass selective (MS) detector

[0289] In FIG. 38, the catalytic conversion of the benzaldehyde is shown as a function of the reaction time is shown. Clearly, all tested supported intermetallic compounds show a significantly higher activity than the support material alone.

BRIEF DESCRIPTION OF THE FIGURES

[0290] FIG. 1: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.1. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0291] FIG. 2: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.2. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0292] FIG. 3: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.3. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0293] FIG. 4: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.4. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0294] FIG. 5: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.5. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0295] FIG. 6: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.6. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0296] FIG. 7: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.7. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0297] FIG. 8: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 1.8. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0298] FIG. 9: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.1.1. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0299] FIG. 10: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.1.2. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0300] FIG. 11: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.1.3. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0301] FIG. 12: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.1.4. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0302] FIG. 13: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.1.5. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0303] FIG. 14: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.1.6. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0304] FIG. 15: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.2.1. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0305] FIG. 16: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.2.2. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0306] FIG. 17: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.2.3. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0307] FIG. 18: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.2.4. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0308] FIG. 19: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.2.5. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0309] FIG. 20: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.2.6. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0310] FIG. 21: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.1. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0311] FIG. 22: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.2. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0312] FIG. 23: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.3. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0313] FIG. 24: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.4. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0314] FIG. 25: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.5. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0315] FIG. 26: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.6. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0316] FIG. 27: shows the X-ray diffraction pattern (copper K alpha radiation) of the supported intermetallic compound according to Example 2.3.7. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0317] FIG. 28: shows the crystallite size (in nm) of the Heusler compounds of Examples 2.3.1 to 2.3.4 determined according to Reference Example 1.2 as a function of the metal content (in weight-%) of the respective compounds.

[0318] FIG. 29: shows 2 TEM images of the particles of the intermetallic compound of Example 2.1.6. In the left image, the scale bar in the right lower corner represents 1 micrometer. In the right image, the scale bar in the right lower corner represents 200 nm.

[0319] FIG. 30: shows 2 TEM images of the particles of the intermetallic compound of Example 2.3.1. In the left image, the scale bar in the right lower corner represents 1 micrometer. In the right image, the scale bar in the right lower corner represents 1 micrometer.

[0320] FIG. 31: shows 2 TEM images of the particles of the intermetallic compound of Example 2.3.4. In the left image, the scale bar in the right lower corner represents 1 micrometer. In the right image, the scale bar in the right lower corner represents 200 nm.

[0321] FIG. 32: shows the yields (Y/%) of cyclohexanone (CHO) and cyclohexanole (CHOL) obtained when using the intermetallic compounds of Examples 1.1 to 1.4 (Co.sub.2CrAl/ZSM-5, Co.sub.2CrGa/ZSM-5, Co.sub.2CrIn/ZSM-5, Co.sub.2CrZn/ZSM-5), as described in Example 3, as a function of the reaction time (t/min), as follows: [0322] filled square: Co.sub.2CrAl/ZSM-5, yield (CHO) [0323] empty square: Co.sub.2CrAl/ZSM-5, yield (CHOL) [0324] filled diamond: Co.sub.2CrGa/ZSM-5, yield (CHO) [0325] empty diamond: Co.sub.2CrGa/ZSM-5, yield (CHOL) [0326] filled triangle tip down: Co.sub.2CrIn/ZSM-5, yield (CHO) [0327] empty triangle tip down: Co.sub.2CrIn/ZSM-5, yield (CHOL) [0328] filled circle: Co.sub.2CrZn/ZSM-5, yield (CHO) [0329] empty circle: Co.sub.2CrZn/ZSM-5, yield (CHOL) [0330] filled triangle tip up: ZSM-5, yield (CHO) [0331] empty triangle tip up: ZSM-5, yield (CHOL)

[0332] FIG. 33: shows the yields (Y/%) of cyclohexanone (CHO) and cyclohexanole (CHOL) obtained when using the intermetallic compounds of Examples 1.5 to 1.8 (Cu.sub.2CoAl/ZSM-5, Cu.sub.2CoGa/ZSM-5, Cu.sub.2CoIn/ZSM-5, Cu.sub.2CoZn/ZSM-5), as described in Example 3, as a function of the reaction time (t/min), as follows: [0333] filled square: Cu.sub.2CoAl/ZSM-5, yield (CHO) [0334] empty square: Cu.sub.2CoAl/ZSM-5, yield (CHOL) [0335] filled diamond, dashed line: Cu.sub.2CoGa/ZSM-5, yield (CHO) [0336] empty diamond, dashed line: Cu.sub.2CoGa/ZSM-5, yield (CHOL) [0337] filled diamond, dotted line: Cu.sub.2CoIn/ZSM-5, yield (CHO) [0338] empty diamond, dotted line: Cu.sub.2CoIn/ZSM-5, yield (CHOL) [0339] filled circle: Cu.sub.2CoZn/ZSM-5, yield (CHO) [0340] empty circle: Cu.sub.2CoZn/ZSM-5, yield (CHOL) [0341] filled triangle tip up: ZSM-5, yield (CHO) [0342] empty triangle tip up: ZSM-5, yield (CHOL)

[0343] FIG. 34: shows the results of FIGS. 33 and 34 in condensed form. For each catalyst (from left to right: Co.sub.2CrAl/ZSM-5, Co.sub.2CrIn/ZSM-5, Co.sub.2CrZn/ZSM-5, Co.sub.2CrGa/ZSM-5, Cu.sub.2CoAl/ZSM-5, Cu.sub.2CoGa/ZSM-5, Cu.sub.2CoIn/ZSM-5, Cu.sub.2CoZn/ZSM-5, ZSM-5), the yields/% are shown in a separate column wherein the lower part of the column shows yield (CHO), the upper part of the column shows yield (CHOL) FIG. 35: shows the catalytic conversion of cinnamaldehyde in the hydrogenation reaction according to Example 4.1 using the supported intermetallic compounds of [0344] Example 2.1.6 (30 weight-% Cu.sub.2NiSn/SiO.sub.2)symbol: black filled circle [0345] Example 2.3.1 (30 weight-% Cu.sub.2NiSn/SiO.sub.2)symbol: black filled triangle tip up [0346] Example 2.3.4 (30 weight-% Cu.sub.2NiSn/SiO.sub.2)symbol: black filled triangle tip down

[0347] FIG. 36: shows the conversion (X; symbol: bullet point (filled circle)) and the selectivities (S) of the three tested supported intermetallic compounds according to Example 4.1. For each catalyst, the selectivity with respect to HZAH and the selectivity with respect to ZAO are shown from left to right in individual columns. The two columns on the left refer to the selectivities the supported intermetallic compound of Example 2.1.6, the two columns in the middle refer to the selectivities the supported intermetallic compound of Example 2.3.1, the two columns on the right refer to the selectivities the supported intermetallic compound of Example 2.3.4. The selectivity with respect to HZAO was 0% for all tested supported intermetallic compounds.

[0348] FIG. 37: shows the conversion (X; symbol: bullet point (filled circle)) and the selectivities (S) of the three tested supported intermetallic compounds according to Example 4.1. For each catalyst, the selectivity with respect to HZAH, the selectivity with respect to ZAO and the selectivity with respect to HZAO are shown from left to right in individual columns. The three columns on the left refer to the selectivities the supported intermetallic compound of Example 2.1.6, the two columns in the middle refer to the selectivities the supported intermetallic compound of Example 2.3.1 (selectivity with respect to HZAO=0), the two columns on the right refer to the selectivities the supported intermetallic compound of Example 2.3.4 (selectivity with respect to HZAO=0).

[0349] FIG. 38: shows the conversion (X) of the six tested supported intermetallic compounds according to Examples 2.1.1 to 2.1.6. The symbols from left to right: [0350] filled square (SiO.sub.2 support) [0351] filled circle (30 weight-% Cu.sub.2NiSn/SiO.sub.2) [0352] filled triangle tip up (30 weight-% Cu.sub.2NiSb/SiO.sub.2) [0353] filled triangle tip down (30 weight-% Cu.sub.2NiAl/SiO.sub.2) [0354] filled diamond (30 weight-% Cu.sub.2NiIn/SiO.sub.2) [0355] filled triangle tip left (30 weight-% Cu.sub.2NiSi/SiO.sub.2) [0356] filled triangle tip right (30 weight-% Cu.sub.2NiGa/SiO.sub.2)

[0357] FIG. 39: shows the X-ray diffraction pattern (copper K alpha radiation) of the zeolitic material (ZSM-5) used as a support material. On the x axis, the degree values (2theta) are shown, on the y axis, the intensity is shown.

[0358] FIG. 40: shows an SEM image of the zeolitic material (ZSM-5) used as a support material. The scale bar in the middle represents 5 micrometer.

[0359] FIG. 41: shows sum ratio distribution of the Heusler compounds of Examples 2.3.4 and Example 2.3.1 in % as a function of the smallest crystalline size in nm as determined according to Reference Example 1.1. As one can see, FIG. 41 is divided into two parts as highlighted by the two different scales therein along the x axis for the smallest dimension (see break in scale indicated by / in the x axis).

CITED LITERATURE

[0360] WO 2017/029165 A [0361] Hedin et al., Z. physik. Chem. B30 (1935), pages 280-288 [0362] Kojima et al., ACS Omega 2 (2017) pages 147-153 [0363] Senanayake et al. Exploring Heusler alloys as catalysts for ammonia dissociation, August 2016, ISBN: 978-1-369-00770-1 [0364] Okamura et al. Structural, magnetic, and transport properties of full-Heusler alloy Co.sub.2(Cr.sub.1-xFe.sub.x)Al thin films J. Appl. Phys. vol. 96, no. 11, 1 Dec. 2004, pages 6561-6564Kelekar et al. Epitaxial growth of the Heusler alloy Co.sub.2Cr.sub.a-xFe.sub.xAl J. Appl. Phys. Vol. 96, no 1, 1 Jul. 2004, pages 540-543 [0365] Ko et al. Half-metallic Fe.sub.2CrSi and non-metallic Cu.sub.2CrAl Heusler alloys for currentperpendicular-to-plane giant magneto-resistance: First principle and experimental study J. Appl. Phys. Vol 109, no. 7, 17 Mar. 2011, pages 7B1031-7B1033