CN109126871B - Formic acid dehydrogenation catalyst and application thereof - Google Patents
Formic acid dehydrogenation catalyst and application thereof Download PDFInfo
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Abstract
The invention relates to a first-class nailAn acid dehydrogenation catalyst; the catalyst comprises metal and ligand, wherein the metal is iridium, rhodium, ruthenium, cobalt and the like, and the ligand is an amino-substituted oxime ether compound; the catalyst is used for dehydrogenation reaction of formic acid for the first time, and the highest TON can reach 505 multiplied by 10 at 70 DEG C4Is the highest value reported at present, and the highest TON can reach 400 multiplied by 10 at 90 DEG C4Is the highest value reported at that temperature.
Description
Technical Field
The invention relates to a catalyst for formic acid dehydrogenation, in particular to a catalyst generated by a bidentate or polydentate ligand containing an amino-substituted oxime ether imine structure and various metal precursors of iridium, rhodium, ruthenium and cobalt.
Background
Formic acid is widely concerned as a liquid hydrogen storage material at present. The ideal formic acid decomposition hydrogen production catalytic system should have the following conditions: (1) the catalyst is stable, the raw materials are easy to obtain, and the preparation is simple; (2) the reaction is free of solvent or takes water as solvent; (3) no additive is added; (4) can decompose pure formic acid or formic acid with larger concentration; (5) the catalytic efficiency is high; (6) the reaction can be carried out in a large amount, the operation is simple, and additional operations such as protection and the like are not needed. The catalyst used for decomposing formic acid to produce hydrogen in the currently reported homogeneous system is mainly a metal complex of ruthenium, rhodium, iridium, iron and cobalt, and the catalytic system can only meet one or two of the above conditions. They require either the addition of a base to adjust the acidity or basicity of the reaction system or the use of an organic solvent, and most of the reactions require protective measures, requiring degassing of the reaction system before the reaction. Examples of small scale dehydrogenation of small amounts of formic acid are numerous (chem. Soc. Rev.2016,45, 3954-. The following are reported for aqueous systems with TON above 2000000 or pure formic acid dehydrogenation. In 2015, Himeda, Fujita, Mucherman et al reported that TON of 2050000 (ACS Catal.2015,5, 5496-. Later they reported another class of catalysts, complexes of pyridine and imidazolium ligands with iridium (Catal. Sci. technol.,2016,6, 988-The chemo-activity is still low. In 2016, the Kawanami group reported that dehydrogenation of formic acid could reach a TON of 5000000 (ChemSusChem 2016,9,2749-2753), but with 2600h reaction time, the catalytic activity was lower. Williams and his associates use a catalyst formed of iridium and N, P-ligands to catalyze the dehydrogenation of pure formic acid (nat. Commun.2016, DOI:10.1038/ncomms11308) to obtain 2160000 TON by the continued addition of formic acid, which requires the addition of 5% formic acid in sodium formate as an additive to the reaction system. Research group of Li reports that the iridium and tetrahydropyrimidine ligand in-situ generated catalyst can catalyze formic acid dehydrogenation (chem. Eur.J.,2015,21,12592-12595) at 80 ℃, 2400000 TON can be obtained by continuously adding formic acid, and the average reaction rate can reach 17000h-1The above.
From these reports, it is known that these homogeneous catalytic systems can achieve higher TON without adding material in aqueous system, which indicates that the stability of the catalyst is better under the reaction conditions reported by them, but the reaction activity is lower, and it is not suitable for application of rapid large amount of hydrogen. The dehydrogenation of formic acid is an endothermic reaction, and the catalytic activity can be greatly improved by increasing the temperature, but only Li research groups report the catalytic reaction result of the dehydrogenation of a large amount of formic acid in a water phase system at 80 ℃, and the reason is supposed to be that the catalytic systems are unstable at high temperature. In the research, the catalyst formed by the amino-substituted oxime ether ligand and the iridium metal has high activity and high stability for the formic acid dehydrogenation reaction in an aqueous phase system, the TON of 4000000 can be obtained at 90 ℃ through one-time reaction, the catalytic efficiency is greatly improved, the catalytic system can also perform the dehydrogenation reaction on pure formic acid without a solvent, and the catalyst is also effective on a mixture formed by an organic solvent and the formic acid. If necessary, the catalyst can also be carried out at 70 ℃, and the TON of one reaction can reach 5050000. The raw materials for synthesizing the catalyst are cheap, the synthesis steps are simple, and the catalyst is suitable for mass production; the catalyst can be generated in situ, a complex can be prepared before reaction, the reaction operation is simple, no protection and dehydrogenation treatment are needed, the stability is good, and the application in the formic acid dehydrogenation reaction is not reported at home and abroad.
Disclosure of Invention
The invention provides a formic acid dehydrogenation catalyst without additives, wherein the ligand structures A-D in the components of the in-situ generated catalyst and the structures E-G of the prepared complex catalyst are as follows:
r is H or C1-18One or more than two kinds of alkyl;
n is 0 or 1-4
R1H or C1-18One of alkyl radicals or Si (CH)3)3，Si(C2H5)3，Si(CH2Ph)3One or more than two of them;
R2，R3，R4h or C1-18One or more than two kinds of alkyl;
x is one or two of CH or N;
L1the aromatic ring is one or more of phenyl, naphthyl and the like, the number of substituents on the aromatic ring can be 1 to 5, and the substituents can be one or more of methyl, ethyl and isopropyl;
L2,L3,L4＝Cl,CO,H2O,OH,CH3CN,N3one or more of DMF and DMSO;
m is one or more of iridium, rhodium, ruthenium and cobalt;
a is an integer between 1 and 6;
v is one of 0, +1, +2, +3, +4, +5, + 6;
Be-is a negative ion, Be-May be specifically Cl-、Br-、I-、H-、BArF-、NO3 -、BF4 -、PF6 -、 SO4 2-、CO3 2-、PO4 3And CF3SO3 -E charge number, in particular one of 1,2,3,4,5, 6;
v＝a×e。
the catalyst provided by the invention can be generated by the ligand and the metal precursor in situ, and can also be a prepared metal complex, and the two catalysts can be used for the formic acid dehydrogenation reaction and have high activity and high stability. The catalyst provided by the invention is used for dehydrogenation reaction of formic acid, the reaction can be carried out in pure formic acid without solvent or under the condition of solvent, the reaction temperature can be between 20 and 120 ℃, the concentration of the catalyst can be between 0.001 and 3.0mol/L, the concentration of the formic acid can be between 0.001 and 25 mol/L, and the reaction does not need any additive.
Compared with the existing formic acid dehydrogenation catalyst, the invention has the following advantages:
1. the ligand used in the invention has simple structure, easy synthesis, cheap and easily available raw materials, and is suitable for mass synthesis.
2. The catalyst used in the invention can catalyze and decompose formic acid at 90 ℃, has good stability and high catalysis efficiency, and the TON of one-time formic acid decomposition can reach 4000000 at the highest and 5050000 at 70 ℃.
3. The catalyst used in the invention is simple and convenient in experimental operation of decomposing formic acid, does not need protective measures and dehydrogenation treatment, and has practical application prospect.
Detailed Description
To further illustrate the present invention, the following examples are set forth, but the scope of the claims of the present invention is not limited by these examples. Meanwhile, the embodiments only give some conditions for achieving the purpose, but do not mean that the conditions must be satisfied for achieving the purpose.
Example 1
Glyoxaloxime L1 was used as ligand, FA (1.0M,10.0mL),60 ℃.
Weighing [ Cp IrCl ]2]2(4.0mg, 5.0. mu. mol) and L1(1.42mg, 12. mu. mol) were placed in a reagent bottle,purified water 1.0mL is added to prepare the aqueous solution of the in-situ catalyst. A Schlenk reaction tube or bottle was filled with magnetons, water (9.42mL) and formic acid (10mmol,0.38mL), sealed with a rubber stopper, and the tube was branched with a rubber tube; after the reaction bottle is placed in a water bath at 60 ℃ and stirred for 10min, 0.2mL (1.0 mu mol) of the prepared catalyst solution is quickly added into the reaction bottle by using a liquid transfer gun, the reaction bottle is sealed, a rubber hose connected with a branch pipe is immediately introduced into a 500mL measuring cylinder filled with water and inverted in a basin, the timing is started, and gas is collected by a drainage method. Calculating the amount of gas collected per unit time, calculating TON and TOF, V (CO)2) Volume of drained water/2, amount of formic acid substance decomposed M (H)2)＝V(H2) Specific data are shown in example 1 of Table 1.
Example 2
The same as example 1 except that ligand (Z) -N' -hydroxypicolinimide L2 was used in place of L1 for the reaction, the results are shown in example 2 of Table 1.
Example 3
The same as example 1 except that 1, 2-dimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyldimethyl.
Example 4
The same as example 1 except that the ligand 1, 2-diaminoglyoxaloxime L4 was used in place of L1 for the reaction, the results are shown in example 4 of Table 1.
Example 5
The same as example 1 except that the ligand 1, 2-bis (isopropylamino) glyoxaloxime L5 was used in place of L1 for the reaction, the results are given in Table 1, example 5.
Example 6
The same as example 1 except that piperazine-2, 3-dione oxime L6 as ligand was used in place of L1 in the reaction, the results are shown in example 6 of Table 1.
Example 7
The same as example 1 except that ligand 5-methyl-piperazine-2, 3-dione oxime L7 was used in place of L1 for the reaction, the results are shown in example 7 of Table 1.
Example 8
The same as example 1, except that the ligand octahydroquinoxaline-2, 3-dione oxime L8 was used in place of L1 for the reaction, the results are shown in example 8 of Table 1.
Example 9
complete-L7 (2.77mg, 5. mu. mol) was weighed into a reagent bottle, and 5 mL of purified water was added to prepare an aqueous solution of the Complex catalyst. See example 1 for additional work-up and table 1 for example 9 for results.
Example 10
The same as example 9 except that Complexx-L8 was used in place of Complexx-L7 in the reaction, the results are shown in example 10 of Table 1.
Example 11
The same as example 1 except that (2Z,6Z) -N '2, N' 6-dihydroxypyradine-2, 6-bis (carboximidamide) L9 was used in place of L1 for the reaction, the results are shown in example 11 of Table 1.
Example 12
The same as example 1 except that (Z) -N' -hydroxypicolinimide L10 was used in place of L1 for the reaction, the results are shown in example 12 of Table 1.
Example 13
Weighing [ Cp IrCl ]2]2(4.0mg, 5.0. mu. mol) and L6(1.73mg, 12. mu. mol) were placed in a reagent bottle, and 10mL of purified water was added to prepare an aqueous solution of the in situ catalyst. Adding magnetons, formic acid (10.0M, 90mL) into a Schlenk reaction tube or bottle, sealing with a rubber stopper, branching off the rubber tube, and placing the rubber tube into a container containing water; after the reaction bottle is placed in a water bath at 90 ℃ and stirred stably for 40 min, 1.0mL (1.0 mu mol) of the prepared catalyst solution is quickly added into the reaction bottle by a pipette, the reaction bottle is sealed, a rubber hose connected with a branch pipe is immediately led into a water basin and filled with water to form an inverted measuring cylinder, timing is started, after no bubble emerges, reaction time is recorded, and the residual formic acid amount in the reaction bottle is analyzed by ion chromatography. See example 13 of Table 2
Example 14
The same as example 11 except that the amount of formic acid added was 1.8mol (10.0M), the results are shown in example 14 of Table 2.
Example 15
The same as example 11 except that the amount of formic acid added was 2.2mol (10.0M), the results are shown in example 15 of Table 2.
Example 16
The same as example 11 except that the amount of ligand added was 3.16mg and Ir/L6 was 1/2, the results are shown in Table 2, example 16.
Example 17
The same as example 11 except that the amount of ligand added was 6.95mg and Ir/L6 was 1/4.4, the results are shown in Table 2, example 17.
Example 18
The same as example 11 except that 11.06mg of ligand was added and Ir/L6 was 1/7, the results are shown in Table 2, example 18.
Example 19
The same as example 11 except that 3.0mol (12.0M) of formic acid was added and Ir/L6 was 1/4.4, the results are shown in Table 2, example 19.
Example 20
The same as example 11 except that 4.0mol (10.0M) of formic acid was added and Ir/L6 was 1/6, the results are shown in Table 2, example 20.
Example 21
The same procedure as in example 11 except that 5.05mol (10.0M) of formic acid was added and Ir/L6 was 1/6, the reaction was carried out at 70 ℃ to obtain the reaction product shown in Table 2, example 21.
Example 22
The same as example 11 except that 4.0mol (10.0M) of formic acid was added and Ir/L8 was 1/6, the results are shown in Table 2, example 22.
Example 23
The same procedure as in example 11 except that 5.0mol (10.0M) of formic acid was used, and Ir/L8 was 1/6 and reacted at 70 ℃ to obtain the reaction product shown in Table 2, example 23.
Example 24
The same as example 11 except that 1.5mol (15.0M) of formic acid was added and Ir/L6 was 1/6, the results are shown in Table 2, example 24.
Example 25
The same as example 11 except that 1.0mol (20.0M) of formic acid was added and Ir/L6 was 1/6, the results are shown in Table 2, example 25.
Example 26
Weighing [ Cp IrCl ]2]2(4.0mg, 5.0. mu. mol) and L7 (12. mu. mol) were placed in a reagent bottle, and 1.0mL of methanol was added to prepare a methanol solution of the in situ catalyst. A Schlenk reaction tube or bottle was charged with magneton, methanol (9.42mL) and formic acid (10mmol,0.38mL) and sealed with a rubber stopperThe branch pipe is connected with a rubber pipe; after the reaction bottle is placed in a water bath at 60 ℃ and stirred for 10min, 0.2mL (1.0 mu mol) of the prepared catalyst solution is quickly added into the reaction bottle by using a liquid transfer gun, the reaction bottle is sealed, a rubber hose connected with a branch pipe is immediately introduced into a 500mL measuring cylinder filled with water and inverted in a basin, the timing is started, and gas is collected by a drainage method. Calculating the amount of gas collected per unit time, calculating TON and TOF, V (CO)2) Volume of drained water/2, amount of formic acid substance decomposed M (H)2)＝V(H2) The specific data are shown in example 26 of Table 3.
Example 27
The same as example 26 except that ethanol was used in place of methanol, the results are shown in example 27 of Table 3.
Example 28
The same as example 26 except that acetone was used instead of methanol, the results are shown in example 28 of Table 3.
Example 29
The same as example 26 except that dimethylformamide was used in place of methanol, the results are shown in example 29 of Table 3.
Example 30
The same as example 26 except that dimethyl sulfoxide was used in place of methanol, the results are shown in example 30 of Table 3.
Example 31
The same as in example 26 except that pure methanol was replaced with a mixed solvent of water and methanol (v/v: 1/1), the results are shown in example 31 of Table 3.
Example 32
The same as in example 26 except that pure methanol was replaced with a mixed solvent of water and acetone (v/v: 1/1), the results are shown in example 32 of Table 3.
Table 1: effect of ligand Structure on dehydrogenation of formic acida
a:Reaction conditions [ IrCpCl ]2]2(0.5 μmol), Ir/L ═ 1/1.2, aqueous formic acid (1.0M,10.0mL),60 ℃; if not otherwise specified, TOF is calculated from the conversion at 3 minutes after the start of the reaction;b:the reaction was started with a timing of 15 minutes without bubbles, and the conversion was calculated as 20 minutes;c:TOF was calculated from the conversion at 8 minutes after the start of the reaction.
TABLE 2 influence of the amount of ligand on the dehydrogenation of formic acida
a:Reaction conditions the in situ generated catalyst is prepared from [ IrCp Cl2]2And L6, [ IrCpCl ] is formed prior to the reaction2]20.5 mu mol, 10.0M formic acid, 90 ℃;b:formic acid (12.0M);c:70℃；d:l8 as a ligand;e:l8 as a ligand, 70 ℃;f:l6 as ligand, formic acid (15.0M);g:l6 as ligand, formic acid (20.0M).
Table 3: effect of solvent on dehydrogenation of formic acida
a:Reaction conditions Ir-L7, various solutions of formic acid (1.0M,10.0mL),60 ℃; unless otherwise specified, TOF is calculated from the conversion at 3 minutes after the start of the reaction.
The catalyst comprises metal and ligand, wherein the metal is iridium, rhodium, ruthenium, cobalt and the like, and the ligand is an amino-substituted oxime ether compound; the catalyst is used for dehydrogenation reaction of formic acid for the first time, and is used at 70 ℃ under the alkali-free conditionThe highest TON can reach 505 multiplied by 104Is the highest value reported at present, and the highest TON can reach 400 multiplied by 10 at 90 DEG C4Is the highest value reported at that temperature.
Claims (6)
1. A catalyst for dehydrogenating formic acid is a metal complex catalyst generated in situ by a metal precursor and a ligand, or a prepared metal complex catalyst; the metal precursor comprises one or more metal salts of iridium, rhodium, ruthenium and cobalt; the ligand structure is one or more than two of A-D, and the metal complex structure is one or more than two of E-G;
r is H or C1-18One or more than two kinds of alkyl;
n = 0 or 1-4;
R1 = H or C1-18One of alkyl radicals or Si (CH)3)3，Si(C2H5)3，Si(CH2Ph)3One or more than two of them;
R2，R3，R4= H or C1-18One or more than two kinds of alkyl;
x is one of CH or N;
L1= cyclopentadienyl Cp, pentamethylcyclopentadienyl Cp, one or more substituted or unsubstituted aromatic rings, the aromatic ring is one or two of phenyl and naphthyl, the number of substituents on the aromatic ring is 1-5, and the substituents are one or more of methyl, ethyl and isopropyl;
L2, L3, L4 = Cl, CO, H2O, OH, CH3CN, N3one or more of DMF and DMSO;
m = one or more of iridium, rhodium, ruthenium and cobalt;
a is an integer between 1 and 6;
v = 0, +1, +2, +3, +4, +5, + 6;
Be-is a negative ion selected from Cl-、 Br-、 I-、H-、 BArF-、 NO3 -、 BF4 -、 PF6 -、 SO4 2-、 CO3 2-、PO4 3-And CF3SO3 -One of (1);
v = a×e。
2. use of a catalyst as claimed in claim 1 in the dehydrogenation of formic acid, characterized in that: the formic acid is pure formic acid or a mixed solution of the formic acid and other solvents, and the other solvents are one or more than two of water, acetone, methanol, ethanol, dimethylformamide and dimethyl sulfoxide.
3. Use of a catalyst according to claim 2, wherein: the concentration of the formic acid in the mixed solution of the formic acid and other solvents is 0.001-25 mol/L.
4. Use of a catalyst according to claim 3, wherein: the concentration of the formic acid in the mixed solution of the formic acid and other solvents is 0.5-15 mol/L.
5. Use of a catalyst according to claim 2 or 3, wherein: the reaction temperature is 20-120 deg.CoC, the concentration of the catalyst is between 0.001 and 3.0 mol/L.
6. Use of a catalyst according to claim 5, wherein: the reaction temperature is 40-100 DEG CoC, the concentration of the catalyst is 0.05-1 mol/L.
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| CN116284157A (en) * | 2021-12-14 | 2023-06-23 | 中国科学院大连化学物理研究所 | Iridium complex, preparation method and application thereof |
| CN114957339B (en) * | 2022-03-25 | 2023-11-24 | 大连理工大学 | Synthesis method of novel complex and application of complex in catalyzing hydrogen storage and desorption of formic acid |
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| EP2647430A1 (en) * | 2012-04-05 | 2013-10-09 | Commissariat à l'Énergie Atomique et aux Énergies Alternatives | Method for preparing a catalyst mediating H2 evolution, said catalyst and uses thereof |
| CN105772091A (en) * | 2014-12-18 | 2016-07-20 | 中国科学院大连化学物理研究所 | CO2 reduction catalyst and application thereof |
| CN105772090A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院大连化学物理研究所 | Formic acid dehydrogenation catalysts in aqueous system, and application thereof |
| CN106391122A (en) * | 2016-08-16 | 2017-02-15 | 渤海大学 | A synthetic method of a polypyrrole-functionalized cobalt complex composite material and applications of the material |
| CN106413891A (en) * | 2013-12-02 | 2017-02-15 | 阿卜杜拉国王科技大学 | Metal-ligand cooperative catalysis through n-h arm deprotonation/pyridine dearomatiztion for efficient hydrogen generation from formic acid |
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| CN106413891A (en) * | 2013-12-02 | 2017-02-15 | 阿卜杜拉国王科技大学 | Metal-ligand cooperative catalysis through n-h arm deprotonation/pyridine dearomatiztion for efficient hydrogen generation from formic acid |
| CN105772090A (en) * | 2014-12-17 | 2016-07-20 | 中国科学院大连化学物理研究所 | Formic acid dehydrogenation catalysts in aqueous system, and application thereof |
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| CN106391122A (en) * | 2016-08-16 | 2017-02-15 | 渤海大学 | A synthetic method of a polypyrrole-functionalized cobalt complex composite material and applications of the material |
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