CN105032424A - Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst - Google Patents

Catalyst for selective hydrogenation reaction of aromatic nitrocompound and preparation method of catalyst Download PDF

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CN105032424A
CN105032424A CN201510303271.9A CN201510303271A CN105032424A CN 105032424 A CN105032424 A CN 105032424A CN 201510303271 A CN201510303271 A CN 201510303271A CN 105032424 A CN105032424 A CN 105032424A
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compound
carbon
base metal
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陈兵峰
袁国卿
李峰波
黄志军
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Institute of Chemistry CAS
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Abstract

The invention relates to a catalyst for selective hydrogenation reaction of an aromatic nitrocompound and a preparation method of the catalyst. The catalyst consists of a catalyst carrier and active metal coated with carbon, wherein the catalyst carrier includes a carbon-base carrier, SiO2, TiO2 or Al2O3; the active metal is selected from Co, Fe, Ni or Cu and other poor and noble metals. The catalyst is prepared by adopting a Pechini type sol-gel process which comprises the steps of dispersing an active metal precursor to water containing a coordination compound, adding a polyhydric alcohol solution and a macromolecule auxiliary, then adding the carrier, stirring for dispersion, carrying out hydrothermal reaction, separating out solid on the lower layer, and calcining in the inert atmosphere to obtain the catalyst in which carbon coats the active metal. Compared with the prior art, the catalyst can realize the hydrogenation reaction of a substituted aromatic nitrocompound in the mild condition; substrate conversion rate and production selectivity are high; the catalyst has recyclable economy and good application prospect.

Description

A kind of Catalysts and its preparation method for aromatic nitro compound selective hydrogenation
Technical field
The present invention relates to the preparation field of catalyst, particularly relate to a kind of Catalysts and its preparation method for aromatic nitro compound selective hydrogenation.
Background technology
Functionalization arylamine is the important industrial chemicals that a class is transformed by substituted aroma nitro compound, and this compounds is widely used in synthesis medicine, dyestuff, polymer, pesticide, spices and the fine chemical product such as surfactant, biomass fuel.It is common catalytic hydrogenation that arylamine is prepared in nitro compound hydrogenation, and a lot of commercial catalysts all can realize, and as Pd/C, Pt/C or RaneyNi etc., and these catalyst selectivity of product in replacement nitro compound hydrogenation reaction is lower.Therefore successfully realize substituted aroma nitro compound selective hydration and prepare functionalization arylamine, key is to design high performance catalyst.
In recent years, the report about substituted aromatic amines selective hydrogenation is quite a lot of, and the heterogeneous catalyst of bibliographical information is mainly divided into two large classes: 1) noble metal catalyst, as load type gold (WO2007116111-A1; JournalofCatalysis, 265 (2009), 19; GreenChem., 14 (2012), 3164) and platinum catalyst (WO2009071727; CN201210468132.8; JournalofCatalysis, 321 (2015), 7) etc., these noble metal catalyst costs are high, need add auxiliary agent regulation and control selective, and there is the problems such as metal residual in product, significantly limit the practical application of this kind of catalyst.2) base metal catalysts, document (Chem.Com., 48 (2012), 7982) the Fe nanometer particles catalyst utilizing citric acid stable, achieve in water and replace nitro compound selective hydration, because this iron catalyst does not use carrier, therefore be difficult to realize catalyst recycling.Document (NatureChem., 5 (2013), 537; Science, 342 (2013), 1073) utilize similar method to prepare Co respectively 3o 4/ C and Fe 2o 3/ C, is applied to substituted aroma nitro compound selective hydrogenation.Although these two kinds of catalyst all have higher selective, in catalyst preparation process, employ expensive organic nitrogen-containing ligand (1,10-phenanthroline), increase catalyst preparing cost undoubtedly.In addition, this preparation method is only applicable to carbon-based supports, and other Carriers Active is low.Relative to noble metal catalyst, base metal catalysts selective for catalytic hydrogenation is easy to regulation and control, and has the advantages such as the low and Environmental compatibility of cost is good.Therefore, research and develop a kind of simple and easy to get, to the base metal catalysts of system high activity, high selectivity, there is important application value.
Summary of the invention
The object of this invention is to provide a kind of Catalysts and its preparation method for aromatic nitro compound selective hydration and application.This catalyst shows higher conversion ratio and selective in hydrogenation reaction, and in catalyst, active component is coated by carbon-coating, and is dispersed on carrier.Just because of this structure, active metal not oxidation by air, is beneficial to the preservation of catalyst, and has maximally utilised active metal, significantly reduces the cost of catalyst.In addition, reaction condition is gentle, easy and simple to handle.
The technical solution adopted in the present invention is:
For a catalyst for aromatic nitro compound selective hydration, it is characterized in that, described catalyst comprises catalyst carrier and the coated active metal of carbon, and described active metal is base metal.
According to the present invention, described catalyst carrier comprises carbon-based supports, SiO 2, TiO 2or Al 2o 3deng, wherein carbon-based supports is such as active carbon, graphite, CNT or Graphene etc.Preferred catalyst carrier is graphite (such as nano graphite carbon) or colloid SiO 2.
According to the present invention, described base metal be preferably selected from Co, Fe, Ni and Cu etc. one or more, one or more also in preferred Co, Cu, Ni.
According to the present invention, described active metal is 0.01-60wt% relative to the content of catalyst of the present invention, preferred 0.1-40wt%, also preferred 10-32wt%.
According to the present invention, the active metal in described catalyst is coated by carbon-coating, and it is dispersed on carrier.
According to the present invention, described catalyst is the coated Co catalyst of nano graphite carbon; The Ni catalyst that nano graphite carbon is coated; The Cu catalyst that nano graphite carbon is coated and colloid SiO 2coated Co catalyst.
Present invention also offers a kind of preparation method of the catalyst for aromatic nitro compound selective hydration, specifically comprise the steps:
A) base metal precursor compound is mixed with organic ligand compound, obtain metal complex solution;
B) by step a) in the metal complex solution that obtains mix with polyatomic alcohol water solution, pluronic polymer, catalyst carrier;
C) heating steps b) the middle mixture obtained, obtain solid;
D) by step c) in the solid that obtains be placed in inert gas under calcine, obtain catalyst of the present invention.
According to the present invention, described step a) in, described base metal precursor compound is the compound containing base metal, such as, containing one or more the compound in cobalt, iron, nickel and copper etc.; The described compound containing base metal is base-metal salt, such as, be selected from nitrate, sulfate, carbonate, chloride or acetate etc.Described organic ligand compound is preferably organic acid, such as, be selected from citric acid, tartaric acid, malic acid, oxalic acid etc.The mol ratio of described base metal precursor compound and organic ligand compound, preferably in 1:1 to 1:5 scope, can also be within the scope of 1:1.5-1:4.
According to the present invention, described step b) in, described polyatomic alcohol water solution can be glycerine water solution or glycol water; The volume ratio of described polyalcohol and water is preferably in the scope of 6:1 to 1:4.Described pluronic polymer is selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, PolyTHF etc.; Preferred polyethylene glycol.The molecular weight of described pluronic polymer preferably 400 ~ 20000 can also be 1000 ~ 10000.
According to the present invention, preferably, the mass ratio of described organic ligand compound, base metal precursor compound, polyalcohol and pluronic polymer is 1 ~ 5:1:20 ~ 120:1.5 ~ 8, can also be 2 ~ 4:1:30 ~ 100:2 ~ 6.
According to the present invention, described step c) in, described heating-up temperature is 100 ~ 250 DEG C, and the heat time is 10-20h.Preferably, mixture is placed in water heating kettle to heat.Preferred, by step b) in the mixture that obtains first dispersed with stirring at normal temperatures, heat afterwards.Preferably, by the solid drying obtained after heating, such as dried overnight at 100 DEG C.
According to the present invention, described steps d) in, described calcining heat is preferably 500-1000 DEG C, is more preferably 600-900 DEG C; Described calcination time is preferably 1.0-4.0 hour, is more preferably 1.5-3.5h.Preferably, the heating rate being elevated to calcining heat by room temperature is 5-20 DEG C/min.Described inert atmosphere can be nitrogen or argon gas.
Catalyst of the present invention adopts Pechini type sol-gel process to be prepared from.Base metal is coated by carbon-coating, efficiently avoid base metal and contacts with air, prevents its oxidation by air, is beneficial to the preservation of catalyst, and has maximally utilised active metal, significantly reduces the cost of catalyst.This catalyst shows high conversion ratio and selective in hydrogenation reaction.
Present invention also offers the application of described heterogeneous catalyst in aromatic nitro compound selective hydrogenation.
According to the present invention, described hydrogenation reaction is carried out in airtight autoclave, and aromatic nitro compound mixes with solvent, adds catalyst of the present invention (catalyst is without the need to activation), initial pressure in reactor during hydrogen room temperature is 0.1-8Mpa, is preferably 1-4Mpa.Reaction temperature 0-200 DEG C, is preferably 20-180 DEG C, more preferably 90-140 DEG C, also more preferably 100-120 DEG C.Reaction time 1-40 hour, preferred 4-36 hour, also preferred 6-24 hour.
According to the present invention, the solvent in described hydrogenation reaction is one or more in water, oxolane, ethanol, carrene, dioxane, ethyl acetate, DMF, n-hexane, methyl-sulfoxide or toluene.Reactant liquor concentration of substrate is preferably greater than 0.01mol/L.
According to the present invention, described aromatic nitro compound is the compound including the aromatic structure that nitro replaces.Such as substituted or unsubstituted nitroaryl compound, substituted or unsubstituted nitro heteroaryl compound, be preferably nitrobenzene, substituted-nitrobenzene or replace nitro het-eroaromatic, above-mentioned substituting group is one or more, be selected from alkyl, alkoxyl, alkylthio group, amino, hydroxyl, nitro, halogen, aldehyde radical, ketone group, ester group, acid amides, cyano group, alkenyl or alkynyl etc., described multiple substituting groups can be identical or different.
According to the present invention, the mol ratio of described catalyst activity metal and reaction substrate is 1 × 10 -4between 1, preferably between 0.01 to 0.5.
Heterogeneous catalyst of the present invention can recycle repeatedly, its conversion ratio and selectively obviously not decline, and catalyst is easily separated with reactant liquor.
The present invention has the following advantages:
1) the present invention's base metal catalysts of adopting carbon-coating coated, realizes aromatic nitro compound selective hydration, and this catalyst has the advantage of active high, selective height and good stability, can realize higher than ten times reuse, and catalytic performance does not reduce.In addition, reaction condition is gentle, easy and simple to handle.
2) the present invention provides a kind of new method for the highly active base metal catalysts of preparation, and the method has that process is easy, raw material is easy to get and obtain the advantages such as catalyst performance is good, and the active metal obtained on catalyst is coated by carbon-coating, is beneficial to the preservation of catalyst.
Accompanying drawing explanation
Fig. 1 is the X-ray diffractogram of the coated cobalt-base catalyst of the obtained carbon-coating of embodiment 1.
Fig. 2 is the transmission electron microscope picture of the coated cobalt-base catalyst of the obtained carbon-coating of embodiment 1.
Detailed description of the invention
Embodiments of the invention are described below in detail.Embodiment described below is exemplary, only for explaining the present invention, and can not be interpreted as limitation of the present invention.Based on the embodiment in the present invention, the every other embodiment that those of ordinary skill in the art obtain under the prerequisite not making creative work, all belongs to the scope of protection of the invention.
Embodiment 1. is based on the catalyst of Co and nano graphite carbon
Get 20ml distilled water, under stirring, add 1.875g tartaric acid, then add 1.819gCo (NO 3) 26H 2o, then 60ml glycerine water solution (glycerine: water=4:1 is added, volume ratio) and 5.0g polyethylene glycol PEG6000, finally add 0.5g nano graphite carbon, after stirring, be placed in water heating kettle 150 DEG C insulation 13h, after obtaining solid drying, be transferred to the lower 800 DEG C of calcining 2.0h of argon gas in tube furnace, obtain being dispersed in the Co catalyst that carbon-coating on nano graphite carbon is coated, the content of Co is 29.2wt%.
The X-ray diffractogram display of the cobalt-base catalyst that Fig. 1 carbon-coating is coated, active metal cobalt is reduction-state.
Embodiment 2. is based on the catalyst of Ni and nano graphite carbon
Get 20ml distilled water, under stirring, add 1.875g tartaric acid, then add 1.818gNi (NO 3) 26H 2o, then 60ml glycerine water solution (glycerine: water=4:1 is added, volume ratio) and 5.0g polyethylene glycol PEG6000, finally add 0.5g nano graphite carbon, after stirring, be placed in water heating kettle 150 DEG C insulation 13h, after obtaining solid drying, be transferred to the lower 800 DEG C of calcining 2.0h of argon gas in tube furnace, obtain being dispersed in the Ni catalyst that carbon-coating on nano graphite carbon is coated, the content of Ni is 28.0wt%.
The transmission electron microscope picture display of the cobalt-base catalyst that Fig. 2 carbon-coating is coated, active metal cobalt nanometer particle is coated with about 2-5nm carbon-coating.
Embodiment 3. is based on the catalyst of Cu and nano graphite carbon
Get 20ml distilled water, under stirring, add 1.875g tartaric acid, then add 1.51gCu (NO 3) 23H 2o, then 60ml glycerine water solution (glycerine: water=4:1 is added, volume ratio) and 5.0g polyethylene glycol PEG6000, finally add 0.5g nano graphite carbon, after stirring, be placed in water heating kettle 150 DEG C insulation 13h, after obtaining solid drying, be transferred to the lower 800 DEG C of calcining 2.0h of argon gas in tube furnace, obtain being dispersed in the Cu catalyst that carbon-coating on nano graphite carbon is coated, the content of Cu is 30.1wt%.
Embodiment 4. is based on Co and colloid SiO 2catalyst
Get 20ml distilled water, under stirring, add 1.875g tartaric acid, then add 1.819gCo (NO 3) 26H 2o, then adds 60ml glycerine water solution (glycerine: water=4:1, volume ratio) and 5.0g polyethylene glycol PEG6000, finally adds 0.5g colloid SiO 2, after stirring, be placed in water heating kettle 150 DEG C insulation 13h, after obtaining solid drying, be transferred to the lower 800 DEG C of calcining 2.0h of argon gas in tube furnace, obtain being dispersed in colloid SiO 2on the coated Co catalyst of carbon-coating, the content of Co is 29.6wt%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 5. is prepared with embodiment 1 prepares aniline
In 100ml autoclave, add nitrobenzene (123mg), catalyst (20mg) prepared by embodiment 1, oxolane (5ml) and water (0.2ml), after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 100%, and the selective of aniline is greater than 99%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 6. is prepared with embodiment 2 prepares aniline
In 100ml autoclave, add nitrobenzene (123mg), catalyst (20mg) prepared by embodiment 2, oxolane (5ml) and water (0.2ml), after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 99.6%, and the selective of aniline is greater than 99%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 7. is prepared with embodiment 3 prepares aniline
In 100ml autoclave, add nitrobenzene (123mg), catalyst (20mg) prepared by embodiment 3, oxolane (5ml) and water (0.2ml), after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 94.3%, and the selective of aniline is greater than 99%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 8. is prepared with embodiment 4 prepares aniline
In 100ml autoclave, add nitrobenzene (123mg), catalyst (20mg) prepared by embodiment 4, oxolane (5ml) and water (0.2ml), after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 99%, and the selective of aniline is greater than 99%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 9. is prepared with embodiment 1 prepares aniline
In 100ml autoclave, add catalyst (20mg), the water (5ml) of nitrobenzene (123mg), embodiment 1 preparation, after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 100%, and the selective of aniline is greater than 99%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 10. reclaims once with embodiment 5 prepares aniline
Repetition embodiment 5 is reacted the catalyst recovery once, add in 100ml autoclave, add nitrobenzene (123mg), oxolane (5ml) and water (0.2ml) again, after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 100%, and the selective of aniline is greater than 99%.
The catalyst hydrogenation of chloronitrobenzene that embodiment 11. reclaims eight times with embodiment 5 prepares aniline
Repetition embodiment 5 is reacted the catalyst recovery after eight times, add in 100ml autoclave, add nitrobenzene (123mg), oxolane (5ml) and water (0.2ml) again, after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 97.4%, and the selective of aniline is greater than 99%.
Embodiment 12-31
Embodiment 12-31 is the embodiment that the catalyst various substituted aroma nitro compound hydrogenation reaction using embodiment 1 to prepare prepares functionalization amine compound, the operating procedure of embodiment 12-31 is with embodiment 5, and table one gives the reaction condition of embodiment and the reaction yield of correspondence.
Table 1
Cobalt-graphitic carbon catalyst prepared by comparative example infusion process prepares aniline for hydrogenation of chloronitrobenzene
In 100ml autoclave, add nitrobenzene (123mg), cobalt-graphitic carbon catalyst (20mg), oxolane (5ml) and water (0.2ml) prepared by infusion process, after filling exhaust three times with hydrogen, Hydrogen Vapor Pressure is adjusted to 3Mpa, stirring reaction 4.0h at 120 DEG C, release after cooling, reactant liquor gas chromatographic analysis, detecting the conversion ratio obtaining nitrobenzene is 0.
To those skilled in the art, obviously the invention is not restricted to the details of above-mentioned one exemplary embodiment, and when not deviating from spirit of the present invention or essential characteristic, the present invention can be implemented in other specific forms.Therefore, no matter from that, all should embodiment be regarded as exemplary, and be nonrestrictive, scope of the present invention has claims instead of above-mentioned explanation to limit, and all changes be therefore intended in the implication of the equivalency by dropping on claim and scope are included in the present invention.

Claims (10)

1. for a catalyst for aromatic nitro compound selective hydration, it is characterized in that, described catalyst comprises catalyst carrier and the coated active metal of carbon, and described active metal is base metal.
2. catalyst according to claim 1, wherein, described catalyst carrier comprises carbon-based supports, SiO 2, TiO 2or Al 2o 3deng, wherein carbon-based supports is such as active carbon, graphite, CNT or Graphene etc.Preferred catalyst is graphite (such as nano graphite carbon) or colloid SiO 2.
3. catalyst according to claim 1, wherein, described base metal be selected from Co, Fe, Ni and Cu etc. one or more, preferred Co, Cu or Ni.
4. the catalyst according to any one of claim 1-3, wherein, described active metal is 0.01-60wt% relative to the content of described catalyst, preferred 0.1-40wt%, also preferred 10-32wt%.
Preferably, described catalyst is the coated Co catalyst of nano graphite carbon; The Ni catalyst that nano graphite carbon is coated; The Cu catalyst that nano graphite carbon is coated and colloid SiO 2coated Co catalyst.
5. a preparation method for catalyst according to claim 1, specifically comprises the steps:
A) base metal precursor compound is mixed with organic ligand compound, obtain metal complex solution;
B) by step a) in the metal complex solution that obtains mix with polyatomic alcohol water solution, pluronic polymer, catalyst carrier;
C) heating steps b) the middle mixture obtained, obtain solid;
D) by step c) in the solid that obtains be placed in inert gas under calcine, obtain catalyst of the present invention.
6. preparation method according to claim 5, wherein, described step a) in, described base metal precursor compound is the compound containing base metal, such as, containing one or more the compound in cobalt, iron, nickel and copper etc.; The described compound containing base metal is preferably base-metal salt, such as, be selected from nitrate, sulfate, carbonate, chloride or acetate etc.Described organic ligand compound is preferably organic acid, such as, be selected from citric acid, tartaric acid, malic acid, oxalic acid etc.The mol ratio of described base metal precursor compound and organic ligand compound, preferably in 1:1 to 1:5 scope, can also be within the scope of 1:1.5-1:4.
7. the preparation method according to claim 5 or 6, described step b) in, described polyatomic alcohol water solution can be glycerine water solution or glycol water; The volume ratio of described polyalcohol and water is preferably in the scope of 6:1 to 1:4.Described pluronic polymer is selected from polyethylene glycol, polypropylene glycol, polyvinyl alcohol, PolyTHF etc.; Preferred polyethylene glycol.The molecular weight of described pluronic polymer preferably 400 ~ 20000 can also be 1000 ~ 10000.
Preferably, the mass ratio of described organic ligand compound, base metal precursor compound, polyalcohol and pluronic polymer is 1 ~ 5:1:20 ~ 120:1.5 ~ 8, can also be 2 ~ 4:1:30 ~ 100:2 ~ 6.
8. the preparation method according to any one of claim 5-7, wherein, described step c) in, described heating-up temperature is 100 ~ 250 DEG C, and the heat time is 10-20h.Preferably, mixture is placed in water heating kettle to heat.Preferred, by step b) in the mixture that obtains first dispersed with stirring at normal temperatures, heat afterwards.Preferably, by the solid drying obtained after heating, such as dried overnight at 100 DEG C.
Preferably, described steps d) in, described calcining heat is preferably 500-1000 DEG C, is more preferably 600-900 DEG C; Described calcination time is preferably 1.0-4.0 hour, is more preferably 1.5-3.5h.Preferably, the heating rate being elevated to calcining heat by room temperature is 5-20 DEG C/min.Described inert atmosphere can be nitrogen or argon gas.
9. the application of the catalyst described in any one of claim 1-4 in aromatic nitro compound selective hydrogenation.
10. application according to claim 9, wherein said hydrogenation reaction is carried out in airtight autoclave, nitro compound mixes with solvent, add the catalyst (catalyst is without the need to activation) described in any one of claim 1-4, initial pressure in reactor during hydrogen room temperature is 0.1-8Mpa, is preferably 1-4Mpa.Reaction temperature 0-200 DEG C, is preferably 20-180 DEG C, is more preferably 90-140 DEG C, also more preferably 100-120 DEG C.Reaction time 1-40 hour.Preferred 4-36 hour, also preferred 6-24 hour.
Preferably, the solvent in described hydrogenation reaction is one or more in water, oxolane, ethanol, carrene, dioxane, ethyl acetate, DMF, n-hexane, methyl-sulfoxide or toluene.Reactant liquor concentration of substrate is preferably greater than 0.01mol/L.
Preferably, described aromatic nitro compound is substituted or unsubstituted nitroaryl compound, substituted or unsubstituted nitro heteroaryl compound, be preferably nitrobenzene, substituted-nitrobenzene or replace nitro het-eroaromatic, above-mentioned substituting group is one or more, be selected from alkyl, alkoxyl, alkylthio group, amino, hydroxyl, nitro, halogen, aldehyde radical, ketone group, ester group, acid amides, cyano group, alkenyl or alkynyl etc., described multiple substituting groups can be identical or different.
Preferably, the mol ratio of described catalyst activity metal and reaction substrate is 1 × 10 -4between 1, preferably between 0.01 to 0.5.
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