CN110449174A - A kind of preparation method of load type nitrogen oxygen codope porous carbon atom level site catalysts - Google Patents
A kind of preparation method of load type nitrogen oxygen codope porous carbon atom level site catalysts Download PDFInfo
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- CN110449174A CN110449174A CN201910596176.0A CN201910596176A CN110449174A CN 110449174 A CN110449174 A CN 110449174A CN 201910596176 A CN201910596176 A CN 201910596176A CN 110449174 A CN110449174 A CN 110449174A
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- porous carbon
- nitrogen oxygen
- oxygen codope
- codope porous
- atom level
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 125000004432 carbon atom Chemical group C* 0.000 title abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 58
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 38
- 239000003513 alkali Substances 0.000 claims abstract description 24
- 150000003624 transition metals Chemical class 0.000 claims abstract description 23
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 18
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 14
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 48
- 235000010469 Glycine max Nutrition 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 239000012153 distilled water Substances 0.000 claims description 32
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 29
- 235000012054 meals Nutrition 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 26
- 239000000843 powder Substances 0.000 claims description 26
- 239000006185 dispersion Substances 0.000 claims description 20
- 239000002253 acid Substances 0.000 claims description 19
- 150000001721 carbon Chemical group 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000013049 sediment Substances 0.000 claims description 16
- 238000002604 ultrasonography Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 15
- 244000068988 Glycine max Species 0.000 claims description 13
- 239000002893 slag Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 229910002651 NO3 Inorganic materials 0.000 claims description 11
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000000428 dust Substances 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 5
- 239000012266 salt solution Substances 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- -1 alkali metal salt Chemical class 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910019891 RuCl3 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Inorganic materials [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(II) nitrate Inorganic materials [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 claims description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 2
- UAIHPMFLFVHDIN-UHFFFAOYSA-K trichloroosmium Chemical compound Cl[Os](Cl)Cl UAIHPMFLFVHDIN-UHFFFAOYSA-K 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 abstract description 59
- 230000003197 catalytic effect Effects 0.000 abstract description 42
- 239000012855 volatile organic compound Substances 0.000 abstract description 37
- 230000015556 catabolic process Effects 0.000 abstract description 26
- 238000006731 degradation reaction Methods 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 7
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000003993 interaction Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 description 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 20
- 238000011056 performance test Methods 0.000 description 20
- 239000007789 gas Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 229910052697 platinum Inorganic materials 0.000 description 11
- 238000001514 detection method Methods 0.000 description 9
- 230000003647 oxidation Effects 0.000 description 9
- 239000010931 gold Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 235000019198 oils Nutrition 0.000 description 7
- 229910052763 palladium Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 229910052709 silver Inorganic materials 0.000 description 6
- 239000003708 ampul Substances 0.000 description 5
- 239000010953 base metal Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000010970 precious metal Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 230000002779 inactivation Effects 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 229910052707 ruthenium Inorganic materials 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- MBHNWCYEGXQEIT-UHFFFAOYSA-N Fluphenazine hydrochloride Chemical compound Cl.Cl.C1CN(CCO)CCN1CCCN1C2=CC(C(F)(F)F)=CC=C2SC2=CC=CC=C21 MBHNWCYEGXQEIT-UHFFFAOYSA-N 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000003694 hair properties Effects 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 229910001338 liquidmetal Inorganic materials 0.000 description 1
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Inorganic materials [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Inorganic materials [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
-
- B01J35/399—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
Abstract
The invention discloses a kind of preparation methods of load type nitrogen oxygen codope porous carbon atom level site catalysts, the catalyst is using the nitrogen oxygen codope porous carbon with unique cell structure and abundant N, O functional group as carrier, thereon by the load of transition metal active atom, and doped alkali metal and alkaline-earth metal are as promotor, due to the strong interaction between alkali or alkaline earth metal and transition metal active component, X-O is formedx‑Yy(OH)zThe atom level active site (X represents transition metal atoms, and Y represents alkali or alkaline earth metal atom) of structure, makes catalyst catalytic activity with higher, stability and selectivity, can be realized catalytic degradation VOCs under room temperature, degradation effect is preferable.
Description
Technical field
The present invention relates to the preparation methods of catalyst, and in particular to the nitrogen oxygen that a kind of alkali or alkaline earth metal promotes is co-doped with
The preparation method of the atom level site catalysts of miscellaneous porous carbon carrying transition metal atom.
Background technique
Volatile organic contaminant (VOCs) is listed in one of significant contributor of air pollution, and inertial thinking is thought,
The oxidative degradation of VOCs, which is necessarily required to hot conditions (200~400 DEG C) or the input of outside energy, could occur efficient forward direction
Catalysis reaction.Based on such thinking, catalytic burning, heat accumulating type catalytic burning, low temperature plasma, ultraviolet light auxiliary catalysis etc.
Energy input type VOCs clear up technology become technology mainstream, but these methods often energy consumption, safety, in terms of there are one
Fixed deficiency.The room-temperature catalytic oxidation VOCs that degrades has that low energy consumption, highly-safe, investment cost is low, the advantages such as without secondary pollution,
Become most promising VOCs degradation technique.
Although the catalysis oxidation of VOCs is thermodynamically feasible under conditions of in normal temperature and pressure and not by outside energy
(Gibbs free energy is less than 0), but its reaction rate is very slow in reality, this just needs to carry out in terms of kinetics
It breaks through, designing suitable high activated catalyst becomes the key for realizing constant temperature catalyzing.It is activity with single or several atoms
The atom level site catalysts in site are the Disciplinary Frontiers of heterogeneous catalysis, are attracted wide attention.Atom level active sites
Point can reduce the activation energy of oxidation reaction, and promote to generate the active oxygen species of high redox potential, thus normal in room temperature
VOCs oxidizing reaction rate is accelerated in pressure.In addition, the site catalysts of atom level dispersion have high atom utilization,
The uniformity of active site can be improved, and the interaction between active site and carrier can be adjusted well, had higher
Catalytic activity and selectivity.Studies have shown that atom level active site is constructed in transition metal atoms load on a solid carrier
Catalyst has preferable catalytic performance and degradation effect, 106622225 A of Publication No. CN for room-temperature catalytic oxidation VOCs
Chinese patent disclose a kind of monatomic Au catalyst for catalytic degradation VOCs, monatomic Au is supported on TiO2Nanometer
On piece, catalytic activity and service life with higher；The Chinese patent of 106807243 A of Publication No. CN is by modified Pt
It is dispersed in MnO2On, the monatomic catalyst of Pt has been synthesized, room temperature degradation aircraft cabin VOCs is used for, there is preferable removal effect
Fruit.But load type metal atom level site catalysts are during the preparation process often due between metal and metal and carrier
Between weak binding and form cluster, reduce atom utilization, when especially load capacity is higher, prepare atom dispersion catalysis
Agent is more difficult.In addition, since metallic atom price is expensive, so that catalyst preparation cost greatly increases.Therefore, design synthesis
Constant temperature catalyzing degradation VOCs atom level site catalysts also face dispersion degree is low, stability is poor, preparation and reaction the phase
Between precious metal atom reunite inactivation, a series of problems, such as VOCs degradation rate is low, preparation cost is high occurs.
Summary of the invention
The purpose of the present invention is being the shortcomings that overcoming prior art, a kind of catalytic activity with higher, stabilization are provided
Property and selectivity, be used for room-temperature catalytic oxidation degradation VOCs, with high degradation rate alkali or alkaline earth metal promote
Into load type nitrogen oxygen codope porous carbon atom level site catalysts preparation method.
The purpose of the present invention is realized by following scheme:
The preparation method of load type nitrogen oxygen codope porous carbon atom level site catalysts provided by the invention, including
Following steps:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step, using grinder by 10~100g soybean slag grind into powder, successively with mass percent be 3%~
5% HCl solution and distilled water is washed, and impurity and remaining hydrochloric acid in soy meal are removed, big after then filtering
Bean dregs powder is placed in 60~100 DEG C of baking ovens dry 1~4h, finally in a vacuum furnace with 200~400 DEG C of temperature in N2Atmosphere
Middle carbonization obtains soy meal in 1~3 hour；
The soy meal is immersed activation 12 in the KOH solution of 3~10mol/L~for 24 hours by second step, make soy meal with
KOH mass ratio is 2:1~4:1, it is subsequently placed in 40~100 DEG C of baking ovens dry 12~for 24 hours, in N in tube furnace after taking-up2Gas
It is carbonized under atmosphere, the control of tube furnace heating rate is warming up to 600~900 DEG C in 2~5 DEG C/min when carbonization, keeps 2~4h；
Third step, the powder after second step is carbonized naturally cool to 15~40 DEG C, are soaked with the dilute acid soln of 1~3mol/L
Bubble 12~for 24 hours, the powder after guaranteeing carbonization can be submerged by dilute acid soln completely, then it is washed with distilled water to PH=7, and in
Dry 8 in 60~150 DEG C of baking ovens~for 24 hours, nitrogen oxygen codope porous carbon is obtained as carrier；
(2) carrying transition metal active component and alkali or alkaline earth metal promotor, comprising the following steps:
The first step weighs the porous carbon dust of 5~50g nitrogen oxygen codope in 50~500ml distilled water, ultrasonic disperse 0.5
~1h forms the first dispersion liquid；
The salt of transition metal or acid solution are added drop-wise in first dispersion liquid by second step, are stirred with glass bar equal
It is even, obtain the first mixed liquor；Then alkali metal salt soln or alkaline-earth metal salt solution are added drop-wise in first mixed liquor,
The second mixed liquor is obtained after shaking up, make the mass ratio 1:10 of transition metal and nitrogen oxygen codope porous carbon in the second mixed liquor~
1:104, the mass ratio of alkali or alkaline earth metal and nitrogen oxygen codope porous carbon is 1:25~1:104；
The second mixed liquor 0.5~3h of ultrasound is kept transition metal and alkali or alkaline earth metal uniform by third step
It is supported on nitrogen oxygen codope porous carbon support, after ultrasound, 10~30ml of sodium borohydride solution of 0.1~0.5mol/L is added,
Third mixed liquor is formed, and is vigorously stirred, until not generating H2, make the metal ion quilt being supported on nitrogen oxygen codope porous carbon
Reduction, then, third mixed liquor is placed in 60~80 DEG C of oil bath pans, adjusts pH to 6~9 with sodium carbonate liquor under stiring,
2~4h is heated, until moisture is all evaporated to obtain sediment；
The sediment is washed with distilled water suction filtration 3~4 times by the 4th step, is placed in 60~150 DEG C of baking ovens dry 8
~12h finally calcines 2~6h in the muffle furnace that temperature is 300~500 DEG C, obtains load type nitrogen oxygen after natural cooling and be co-doped with
Miscellaneous porous carbon atom level site catalysts.
Present invention has the advantage that
(1) atom level site catalysts provided by the invention are using alkali or alkaline earth metal as promotor, its energy
Enough that strong interaction occurs with transition metal active component that is being supported on carrier surface, forming structure is X-Ox-Yy(OH)zOriginal
Sub- grade active site (X represents transition metal atoms, and Y represents alkali or alkaline earth metal atom), to significantly improve catalysis
The selectivity and catalytic activity of agent make it have high catalytic performance in VOCs oxidation reaction.
(2) doping of alkali or alkaline earth metal can reduce the partial size of carrier surface metallic particles, facilitate transition gold
The dispersion for belonging to active atomic, prevents its aggregation from forming cluster, to promote the formation of atom level active site, urges applied to room temperature
Change degradation VOCs, significantly improves VOCs degradation rate.
(3) atom level site catalysts provided by the invention select nitrogen oxygen codope porous carbon as carrier, before
Body material is the by-product of soybean slag of soybean oil extract, is prepared by simple KOH activation and high temperature cabonization.Soybean slag contains
There is N, O functional group abundant, nitrogen source, oxygen source and carbon source can be used as to have without additionally adding any nitrogen source and oxygen source simultaneously
Raw material sources are wide, preparation section is simple, cost is relatively low, meet the advantages such as Green Sustainable strategy.
(4) the nitrogen oxygen codope porous carbon support that uses of the present invention has a pore structure abundant, higher specific surface area,
The aggregation that can reduce metallic particles keeps higher catalytic activity while stablizing anchoring metallic atom.And nitrogen and oxygen
Doping increase the quantity of defect sites, enhance the interaction between active site and carrier, N and O and active component
It is coordinated the unsaturated structure formed, greatly improves reactivity and selectivity.
(5) since precious metal atom is expensive, traditional noble metal catalyst preparation cost is often higher.And it is of the invention
The atom level site catalysts of offer can also use base metal atom as active component, in addition the precursor material of carrier
Material selects discarded soybean slag, considerably reduces catalyst preparation cost, and preparation section is simple, should for large-scale production
Catalyst economy with higher and feasibility.
(6) atom level site catalysts provided by the invention can keep excellent stability in a long time, make
With lasting a long time, without often more catalyst changeout, the cost of degradation VOCs is greatly reduced.
It (7) can be recyclable again through microwave or high-temperature process after atom level site catalysts inactivation provided by the invention
It is raw, it still can reach VOCs treatment effect before inactivation, not only save economic cost, but also meet Green Sustainable strategy.
(8) atom level site catalysts provided by the invention have for the VOCs in constant temperature catalyzing degradation exhaust gas
Degradation efficiency is high, reaction condition is mild (being not necessarily to high temperature and pressure, can carry out at normal temperatures and pressures), treatment cost is low, safety
The advantages that high, and can be by the thorough catalytic degradation of VOCs at CO2And water, it is without secondary pollution.
(9) the atom level site catalysts provided by the invention low concentration that can be applied under normal temperature and pressure to degrade is waved
One of hair property organic pollutant (VOCs), such as methanol, acetone, ethyl acetate non-aromatic VOCs or a variety of, it is especially suitable
It is 200~1000mg/m for VOCs initial concentration3, degradation rate can reach 80% or more.
Specific embodiment
The present invention is further elaborated below by specific embodiment.
A kind of preparation method of load type nitrogen oxygen codope porous carbon atom level site catalysts, including following step
It is rapid:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step, using grinder by 10~100g soybean slag grind into powder, successively with mass percent be 3%~
5% HCl solution and distilled water is washed, and metal impurities and remaining hydrochloric acid in soy meal are removed, after then filtering
Soybean slag powder is placed in 60~100 DEG C of baking ovens dry 1~4h, finally in a vacuum furnace with 200~400 DEG C of temperature in N2Gas
It is carbonized 1~3 hour in atmosphere and obtains soy meal；
The soy meal is immersed activation 12 in the KOH solution of 3~10mol/L~for 24 hours by second step, make soy meal with
KOH mass ratio is 2:1~4:1.It is subsequently placed in 40~100 DEG C of baking ovens dry 12~for 24 hours, in N in tube furnace after taking-up2Gas
It is carbonized under atmosphere, the control of tube furnace heating rate is warming up to 600~900 DEG C in 2~5 DEG C/min when carbonization, keeps 2~4h；
Third step, the powder after second step is carbonized naturally cool to 15~40 DEG C, are soaked with the dilute acid soln of 1~3mol/L
Bubble 12~for 24 hours, the powder after guaranteeing carbonization can be submerged by dilute acid soln completely.Then it is washed with distilled water to PH=7, and in
Dry 8 in 60~150 DEG C of baking ovens~for 24 hours, nitrogen oxygen codope porous carbon (NOPC) is obtained as carrier.It is impregnated using dilute acid soln
It can achieve following purpose: one, aoxidizing carbon support, increase the oxygen-containing functional group of carbon surface, such as hydroxyl, carboxyl, make carbon
Carrier is more hydrophilic, so that carbon material be made to be easier to be impregnated by metal front liquid solution, two, the metallic atom on dipping is by these
Oxygen-containing functional group is fixed, and is not susceptible to reunite；Three, certain metal impurities are removed, purification is played.
The dilute acid soln can be one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, acetum.
(2) carrying transition metal active component and alkali or alkaline earth metal promotor, comprising the following steps:
The first step weighs the porous carbon dust of 5~50g nitrogen oxygen codope in 50~500ml distilled water, ultrasonic disperse 0.5
~1h forms the first dispersion liquid；
The salt of transition metal or acid solution are added drop-wise in first dispersion liquid by second step, are stirred with glass bar equal
It is even, obtain the first mixed liquor；Then alkali metal salt soln or alkaline-earth metal salt solution are added drop-wise in first mixed liquor,
The second mixed liquor is obtained after shaking up, make the mass ratio 1:10 of transition metal and nitrogen oxygen codope porous carbon in the second mixed liquor~
1:104, the mass ratio of alkali or alkaline earth metal and nitrogen oxygen codope porous carbon is 1:25~1:104；
The salt or acid solution of the transition metal can be H2PtCl6、PdSO4、HAuCl4、AgNO3、RuCl3、Rh
(NO3)3、OsCl3、H2IrCl6、FeCl3、Co(NO3)2、Ni(NO3)2、Cu(NO3)2One or both of Deng；The alkali gold
Belonging to salting liquid or alkaline-earth metal salt solution can be the nitric acid of the nitrate of alkali metal, sulfate, carbonate and alkaline-earth metal
One of salting liquids soluble easily in water such as salt.Transition metal atoms as active component, can for Pt, Pd, Au, Ag, Rh,
The noble metals such as one or both of Ru, Os, Ir, Fe, Co, Ni, Cu etc., preferably Pt, Pd, Au, Ag, Rh, Ru, Os, Ir are former
Son；Alkali or alkaline earth metal as promotor, can for one of Li, Na, K, Rb, Cs, Be, Mg, Ca, Sr, Ba etc. or
Two kinds, the preferably alkaline-earth metal such as Ca, Ba.
The second mixed liquor 0.5~3h of ultrasound is kept transition metal and alkali or alkaline earth metal uniform by third step
It is supported on nitrogen oxygen codope porous carbon support.After ultrasound, 10~30ml of sodium borohydride solution of 0.1~0.5mol/L is added,
Third mixed liquor is formed, and is vigorously stirred, until not generating H2, make the metal ion quilt being supported on nitrogen oxygen codope porous carbon
Reduction.Then, third mixed liquor is placed in 60~80 DEG C of oil bath pans, adjusts pH to 6~9 with sodium carbonate liquor under stiring,
2~4h is heated, until moisture is all evaporated to obtain sediment.
The sediment is washed with distilled water suction filtration 3~4 times by the 4th step, is placed in 60~150 DEG C of baking ovens dry 8
~12h finally calcines 2~6h in the muffle furnace that temperature is 300~500 DEG C, obtains load type nitrogen oxygen after natural cooling and be co-doped with
Miscellaneous porous carbon atom level site catalysts.
Embodiment 1
The preparation of 2%Ca-5%Pt/NOPC atom level site catalysts:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step, HCl solution and steaming using grinder by 50g soybean slag grind into powder, with mass percent for 4%
Distilled water is washed, and metal impurities and hydrochloric acid Liquid Residue in soy meal are removed, and is subsequently placed in 80 DEG C of baking ovens dry 2h, most
Afterwards in a vacuum furnace with 300 DEG C of temperature in N2It is carbonized 2 hours in atmosphere；
The soy meal is immersed in the KOH solution of 8mol/L and activates 18h, makes soy meal and KOH mass ratio by second step
For 3:1.Dry 20h is subsequently placed in 80 DEG C of baking ovens, in N in tube furnace after taking-up2It is carbonized under atmosphere, tubular type when carbonization
The control of furnace heating rate is warming up to 700 DEG C in 4 DEG C/min, keeps 3h；
Third step, the powder after second step is carbonized naturally cool to 30 DEG C, are impregnated with the dilute hydrochloric acid solution of 2mol/L
20h, the powder after guaranteeing carbonization can be submerged by dilute acid soln completely.Then it is washed with distilled water to PH=7, and is dried in 80 DEG C
Dry 20h in case, obtains nitrogen oxygen codope porous carbon (NOPC) as carrier.
(2) precious metals pt and alkaline-earth metal Ca are supported on nitrogen oxygen codope porous carbon, comprising the following steps:
The first step weighs the porous carbon dust of 25g nitrogen oxygen codope in 300ml distilled water, ultrasonic disperse 45min, is formed
First dispersion liquid；
Second step, by H2PtCl6Solution is added drop-wise in first dispersion liquid, is stirred evenly with glass bar, is obtained first
Mixed liquor；Then by Ca (NO3)2Solution is added drop-wise in first mixed liquor, and the second mixed liquor is obtained after shaking up, makes second
The mass ratio of Pt and nitrogen oxygen codope porous carbon is 1:20 in mixed liquor, and the mass ratio of Ca and nitrogen oxygen codope porous carbon are 1:
50；
The second mixed liquor ultrasound 2h is made Pt and Ca uniform load on nitrogen oxygen codope porous carbon by third step.
After ultrasound, the sodium borohydride solution 20ml of 0.2mol/L is added, forms third mixed liquor, and be vigorously stirred, until not generating H2,
Make the Pt being supported on nitrogen oxygen codope porous carbon4+And Ca2+It is reduced.Then, third mixed liquor is placed in 70 DEG C of oil bath pans
In, pH to 7 is adjusted with sodium carbonate liquor under stiring, heats 3h, until moisture is all evaporated to obtain sediment.
The sediment is washed with distilled water suction filtration 3 times by the 4th step, is placed in dry 10h in 80 DEG C of baking ovens, is finally existed
4h is calcined in the muffle furnace that temperature is 400 DEG C, load type nitrogen oxygen codope porous carbon atom level active sites are obtained after natural cooling
Site catalyst.
The 2%Ca-5%Pt/NOPC atom level site catalysts of above-mentioned preparation are placed in fixed-bed reactor
The catalytic performance test for carrying out ozone oxidation degradation methanol, toluene, acetoneand ethyl acetate, it is 8mm that catalyst, which is put into internal diameter,
Quartz ampoule in tested, the length of catalyst reaction device is 30cm, online using the gas chromatograph equipped with fid detector
Concentration after the initial concentration of detection VOCs and reaction uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control
Make as follows: VOCs initial concentration is 200~1000mg/m3, ozone inlet concentration is 800mg/m3, reaction temperature is 25 DEG C, gas
Precursor reactant air speed is 24000h-1.The catalytic performance test result of 2%Ca-5%Pt/NOPC atom level site catalysts is such as
Shown in table 1.
1 2%Ca-5%Pt/NOPC atom level site catalysts catalytic performance test result of table
Embodiment 2
The preparation of 1%Ba-3%Pd/NOPC atom level site catalysts:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step is washed with 3%HCl solution and distilled water, is removed using grinder by 30 soybean slag grind into powder
Metal impurities and hydrochloric acid Liquid Residue in soy meal are removed, dry 2h is subsequently placed in 100 DEG C of baking ovens, finally in a vacuum furnace 300
In N at a temperature of DEG C2Be carbonized 2h in atmosphere；
The soy meal is immersed in the KOH solution of 6mol/L and activates 18h, makes soy meal and KOH mass ratio by second step
For 4:1.Dry 18h is subsequently placed in 60 DEG C of baking ovens, in N in tube furnace after taking-up2It is carbonized under atmosphere, tubular type when carbonization
The control of furnace heating rate is warming up to 900 DEG C in 2 DEG C/min, keeps 2h；
Third step, the powder after second step is carbonized naturally cool to 25 DEG C, are impregnated with the dilute phosphoric acid solution of 3mol/L
12h, the powder after guaranteeing carbonization can be submerged by dilute acid soln completely.Then it is washed with distilled water to PH=7, and in 150 DEG C
Dry 12h in baking oven, obtains nitrogen oxygen codope porous carbon (NOPC) as carrier.
(2) precious metals pd and alkaline-earth metal Ba are supported on nitrogen oxygen codope porous carbon, comprising the following steps:
The first step weighs the porous carbon dust of 15g nitrogen oxygen codope in 150ml distilled water, ultrasonic disperse 30min, is formed
First dispersion liquid；
Second step, by PdSO4Solution is added drop-wise in first dispersion liquid, is stirred evenly with glass bar, is obtained first
Mixed liquor；Then by Ba (NO3)2Solution is added drop-wise in first mixed liquor, and the second mixed liquor is obtained after shaking up, makes second
The mass ratio of Pd and nitrogen oxygen codope porous carbon is 1:33.3 in mixed liquor, and the mass ratio of Ba and nitrogen oxygen codope porous carbon are 1:
100；
The second mixed liquor ultrasound 1h is made Pd and Ba uniform load on nitrogen oxygen codope porous carbon by third step.
After ultrasound, the sodium borohydride solution 20ml of 0.2mol/L is added, forms third mixed liquor, and be vigorously stirred, until not generating H2,
Make the Pd being supported on nitrogen oxygen codope porous carbon2+And Ba2+It is reduced.Then, third mixed liquor is placed in 80 DEG C of oil bath pans
In, pH to 7 is adjusted with sodium carbonate liquor under stiring, heats 2h, until moisture is all evaporated to obtain sediment.
The sediment is washed with distilled water suction filtration 4 times by the 4th step, is placed in dry 8h in 100 DEG C of baking ovens, is finally existed
3h is calcined in the muffle furnace that temperature is 500 DEG C, load type nitrogen oxygen codope porous carbon atom level active sites are obtained after natural cooling
Site catalyst.
The 1%Ba-3%Pd/NOPC atom level site catalysts of above-mentioned preparation are placed in fixed-bed reactor
The catalytic performance test for carrying out ozone oxidation degradation methanol, toluene, acetoneand ethyl acetate, it is 8mm that catalyst, which is put into internal diameter,
Quartz ampoule in tested, the length of catalyst reaction device is 30mm, online using the gas chromatograph equipped with fid detector
Concentration after the initial concentration of detection VOCs and reaction uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control
Make as follows: VOCs initial concentration is 200~1000mg/m3, ozone inlet concentration is 800mg/m3, reaction temperature is 25 DEG C, gas
Precursor reactant air speed is 24000h-1.The catalytic performance test result of 1%Ba-3%Pd/NOPC atom level site catalysts is such as
Shown in table 2.
2 1%Ba-3%Pd/NOPC atom level site catalysts catalytic performance test result of table
Embodiment 3
The preparation of 0.01%K-0.01%Ag/NOPC atom level site catalysts:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step is successively 3%HCl solution using mass percent using grinder by 10g soybean slag grind into powder
It is washed with distilled water, removes the metal impurities and hydrochloric acid Liquid Residue in soy meal, be subsequently placed in 60 DEG C of baking ovens dry 4h,
Finally in a vacuum furnace at a temperature of 200 DEG C in N2It is carbonized 3 hours in atmosphere；
The soy meal is immersed in the KOH solution of 3mol/L and is activated for 24 hours, makes soy meal and KOH mass ratio by second step
For 2:1.It is subsequently placed in 40 DEG C of baking ovens and dries for 24 hours, in N in tube furnace after taking-up2It is carbonized under atmosphere, tubular type when carbonization
The control of furnace heating rate is warming up to 600 DEG C in 2 DEG C/min, keeps 4h；
Third step, the powder after second step is carbonized naturally cool to 15 DEG C, are impregnated with the dilute nitric acid solution of 1mol/L
12h, the powder after guaranteeing carbonization can be submerged by dilute acid soln completely.Then it is washed with distilled water to PH=7, and is dried in 60 DEG C
Drying for 24 hours, obtains nitrogen oxygen codope porous carbon (NOPC) as carrier in case.
(2) precious metals ag and alkali metal K are supported on nitrogen oxygen codope porous carbon, comprising the following steps:
The first step weighs the porous carbon dust of 5g nitrogen oxygen codope in 50ml distilled water, ultrasonic disperse 30min, forms the
One dispersion liquid；
Second step, by AgNO3Solution is added drop-wise in first dispersion liquid, is stirred evenly with glass bar, is obtained first
Mixed liquor；Then by KNO3Solution is added drop-wise in first mixed liquor, and the second mixed liquor is obtained after shaking up, makes the second mixing
The mass ratio of Ag and nitrogen oxygen codope porous carbon is 1:10 in liquid4, the mass ratio of K and nitrogen oxygen codope porous carbon is 1:104；
The second mixed liquor ultrasound 0.5h is made Ag and K uniform load in nitrogen oxygen codope porous carbon by third step
On.After ultrasound, the sodium borohydride solution 10ml of 0.1mol/L is added, forms third mixed liquor, and be vigorously stirred, until not generating
H2, make the Ag being supported on nitrogen oxygen codope porous carbon+And K+It is reduced.Then, third mixed liquor is placed in 60 DEG C of oil bath pans
In, pH to 6 is adjusted with sodium carbonate liquor under stiring, heats 2h, until moisture is all evaporated to obtain sediment.
The sediment is washed with distilled water suction filtration 3 times by the 4th step, is placed in dry 12h in 60 DEG C of baking ovens, is finally existed
6h is calcined in the muffle furnace that temperature is 300 DEG C, load type nitrogen oxygen codope porous carbon atom level active sites are obtained after natural cooling
Site catalyst.
Fixed bed reaction dress is placed in the 0.01%K-0.01%Ag/NOPC atom level site catalysts of above-mentioned preparation
The catalytic performance test of middle progress ozone oxidation degradation methanol, toluene, acetoneand ethyl acetate is set, catalyst, which is put into internal diameter, is
It is tested in the quartz ampoule of 8mm, the length of catalyst reaction device is 30mm, uses the gas chromatograph that fid detector is housed
Concentration after the initial concentration of on-line checking VOCs and reaction uses the inlet and outlet concentration of ozone analyzer detection ozone.React item
Part control is as follows: VOCs initial concentration is 200~1000mg/m3, ozone inlet concentration is 800mg/m3, reaction temperature 25
DEG C, gas reaction air speed is 24000h-1.The catalytic performance test of 0.5%K-2%Ag/NOPC atom level site catalysts
The results are shown in Table 3.
3 0.01%K-0.01%Ag/NOPC atom level site catalysts catalytic performance test result of table
Embodiment 4
The preparation of 1%Mg-4%Cu/NOPC atom level site catalysts:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step, using grinder by 60g soybean slag grind into powder, the HCl solution for the use of mass fraction being successively 4%
It is washed with distilled water, removes the metal impurities and hydrochloric acid Liquid Residue in soy meal, be subsequently placed in 60 DEG C of baking ovens dry 4h,
Finally in a vacuum furnace at a temperature of 300 DEG C in N2It is carbonized 2 hours in atmosphere；
The soy meal is immersed in the KOH solution of 6mol/L and activates 20h, makes soy meal and KOH mass ratio by second step
For 4:1.Dry 20h is subsequently placed in 80 DEG C of baking ovens, in N in tube furnace after taking-up2It is carbonized under atmosphere, tubular type when carbonization
The control of furnace heating rate is warming up to 700 DEG C in 5 DEG C/min, keeps 4h；
Third step, the powder after second step is carbonized naturally cool to 30 DEG C, are impregnated with the dilute acetic acid solution of 3mol/L
15h, the powder after guaranteeing carbonization can be submerged by dilute acid soln completely.Then it is washed with distilled water to PH=7, and is dried in 80 DEG C
Dry 20h in case, obtains nitrogen oxygen codope porous carbon (NOPC) as carrier.
(2) base metal Cu and alkaline-earth metal Mg are supported on nitrogen oxygen codope porous carbon, comprising the following steps:
The first step weighs the porous carbon dust of 30g nitrogen oxygen codope in 300ml distilled water, ultrasonic disperse 1h, forms first
Dispersion liquid；
Second step, by Cu (NO3)2Solution is added drop-wise in first dispersion liquid, is stirred evenly with glass bar, obtains the
One mixed liquor；Then by Mg (NO3)2Solution is added drop-wise in first mixed liquor, and the second mixed liquor is obtained after shaking up, and makes the
The mass ratio of Cu and nitrogen oxygen codope porous carbon is 1:25 in two mixed liquors, and the mass ratio of Mg and nitrogen oxygen codope porous carbon are 1:
100；
The second mixed liquor ultrasound 3h is made Cu and Mg uniform load on nitrogen oxygen codope porous carbon by third step.
After ultrasound, the sodium borohydride solution 10ml of 0.5mol/L is added, forms third mixed liquor, and be vigorously stirred, until not generating H2,
Make the Cu being supported on nitrogen oxygen codope porous carbon2+And Mg2+It is reduced.Then, third mixed liquor is placed in 60 DEG C of oil bath pans
In, pH to 7 is adjusted with sodium carbonate liquor under stiring, heats 4h, until moisture is all evaporated to obtain sediment.
The sediment is washed with distilled water suction filtration 4 times by the 4th step, is placed in dry 10h in 80 DEG C of baking ovens, is finally existed
2h is calcined in the muffle furnace that temperature is 500 DEG C, load type nitrogen oxygen codope porous carbon atom level active sites are obtained after natural cooling
Site catalyst.
The 1%Mg-4%Cu/NOPC atom level site catalysts of above-mentioned preparation are placed in fixed-bed reactor
The catalytic performance test for carrying out ozone oxidation degradation methanol, toluene, acetoneand ethyl acetate, it is 8mm that catalyst, which is put into internal diameter,
Quartz ampoule in tested, the length of catalyst reaction device is 30mm, online using the gas chromatograph equipped with fid detector
Concentration after the initial concentration of detection VOCs and reaction uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control
Make as follows: VOCs initial concentration is 200~1000mg/m3, ozone inlet concentration is 800mg/m3, reaction temperature is 25 DEG C, gas
Precursor reactant air speed is 24000h-1.The catalytic performance test result of 1%Mg-4%Cu/NOPC atom level site catalysts is such as
Shown in table 4.
4 1%Mg-4%Cu/NOPC atom level site catalysts catalytic performance test result of table
Embodiment 5
The preparation of 4%Li-10%Co/NOPC atom level site catalysts:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step, using grinder by 100g soybean slag grind into powder, the HCl solution for being successively 5% with mass fraction
It is washed with distilled water, removes the metal impurities and hydrochloric acid Liquid Residue in soy meal, be subsequently placed in 100 DEG C of baking ovens dry
1h, finally in a vacuum furnace at a temperature of 400 DEG C in N2It is carbonized 1 hour in atmosphere；
The soy meal is immersed in the KOH solution of 10mol/L and activates 12h, makes soy meal and KOH mass by second step
Than for 4:1.Dry 12h is subsequently placed in 100 DEG C of baking ovens, in N in tube furnace after taking-up2It is carbonized under atmosphere, when carbonization
The control of tube furnace heating rate is warming up to 900 DEG C in 5 DEG C/min, keeps 2h；
Third step, the powder after second step is carbonized naturally cool to 40 DEG C, are impregnated with the dilution heat of sulfuric acid of 3mol/L
For 24 hours, guarantee that the powder after carbonization can be submerged by dilute acid soln completely.Then it is washed with distilled water to PH=7, and in 150 DEG C
Dry 8h in baking oven, obtains nitrogen oxygen codope porous carbon (NOPC) as carrier.
(2) base metal Co and alkali metal Li are supported on nitrogen oxygen codope porous carbon, comprising the following steps:
The first step weighs the porous carbon dust of 50g nitrogen oxygen codope in 500ml distilled water, ultrasonic disperse 1h, forms first
Dispersion liquid；
Second step, by Co (NO3)2Solution is added drop-wise in first dispersion liquid, is stirred evenly with glass bar, obtains the
One mixed liquor；Then by LiNO3Solution is added drop-wise in first mixed liquor, and the second mixed liquor is obtained after shaking up, makes second
The mass ratio of Co and nitrogen oxygen codope porous carbon is 1:10 in mixed liquor, and the mass ratio of Li and nitrogen oxygen codope porous carbon are 1:
25；
The second mixed liquor ultrasound 3h is made Co and Li uniform load on nitrogen oxygen codope porous carbon by third step.
After ultrasound, the sodium borohydride solution 30ml that 0.5mol/L is added forms third mixed liquor, and is vigorously stirred, until not generating H2,
Make the Co being supported on nitrogen oxygen codope porous carbon2+And Li+It is reduced.Then, third mixed liquor is placed in 80 DEG C of oil bath pans,
PH to 9 is adjusted with sodium carbonate liquor under stiring, heats 4h, until moisture is all evaporated to obtain sediment.
The sediment is washed with distilled water suction filtration 4 times by the 4th step, is placed in dry 8h in 150 DEG C of baking ovens, is finally existed
2h is calcined in the muffle furnace that temperature is 500 DEG C, load type nitrogen oxygen codope porous carbon atom level active sites are obtained after natural cooling
Site catalyst.
The 4%Li-10%Co/NOPC atom level site catalysts of above-mentioned preparation are placed in fixed-bed reactor
The catalytic performance test for carrying out ozone oxidation degradation methanol, toluene, acetoneand ethyl acetate, it is 8mm that catalyst, which is put into internal diameter,
Quartz ampoule in tested, the length of catalyst reaction device is 30mm, online using the gas chromatograph equipped with fid detector
Concentration after the initial concentration of detection VOCs and reaction uses the inlet and outlet concentration of ozone analyzer detection ozone.Reaction condition control
Make as follows: VOCs initial concentration is 200~1000mg/m3, ozone inlet concentration is 800mg/m3, reaction temperature is 25 DEG C, gas
Precursor reactant air speed is 24000h-1.The catalytic performance test result of 3%Li-5%Co/NOPC atom level site catalysts is such as
Shown in table 5.
5 4%Li-10%Co/NOPC atom level site catalysts catalytic performance test result of table
Comparative example 1
The alkaline-earth metal Ca promotor of embodiment 1 is changed to Alkali-Metal Na, i.e. Ca (NO in step (2)3)2Solution replaces with
NaNO3Solution, and 2%Na-5%Pt/NOPC atom level site catalysts are prepared according to the method for embodiment 1, and in phase
Its catalytic performance is tested under same reaction condition, test result is recorded in table 6.
6 2%Na-5%Pt/NOPC atom level site catalysts catalytic performance test result of table
Comparative example 2
The noble metal active component Pt of embodiment 1 is changed to base metal active component Ni, i.e. H in step (2)2PtCl6It is molten
Liquid replaces with Ni (NO3)2Solution, and the catalysis of 2%Ca-5%Ni/NOPC atom level active site is prepared according to the method for embodiment 1
Agent, and its catalytic performance is tested under identical reaction conditions, test result is recorded in table 7.
7 2%Ca-5%Ni/NOPC atom level site catalysts catalytic performance test result of table
Comparative example 3
It is added without alkali or alkaline earth metal promotor, it is living according to the method preparation 5%Pt/NOPC atom level of comparative example 1
Property site catalyst, and its catalytic performance is tested under identical reaction conditions, test result is recorded in table 8.
8 5%Pt/NOPC atom level site catalysts catalytic performance test result of table
Comparative example 4
It is added without alkali or alkaline earth metal promotor, it is living according to the method preparation 5%Ni/NOPC atom level of comparative example 2
Property site catalyst, and its catalytic performance is tested under identical reaction conditions, test result is recorded in table 9.
9 5%Ni/NOPC atom level site catalysts catalytic performance test result of table
By the catalyst sample in embodiment and comparative example to methanol, toluene, acetoneand ethyl acetate average degradation rate
It is aggregated into table 10.
Each atom level site catalysts catalytic performance test of table 10 compares
As can be seen from the above table, the load type nitrogen oxygen codope porous carbon atom level site catalysts that alkali metal promotes
90% or more can be reached to the simple non-aromatic VOCs degradation rate of the structures such as methanol, acetoneand ethyl acetate, and for knot
The toluene of structure complexity, degradation rate are also able to maintain 80% or more.Therefore, atom level site catalysts of the present invention exist
All there is preferable removal effect to a variety of VOCs under normal temperature and pressure.In addition, the test result from embodiment 1 and comparative example 1 can
To find out, identical transition metal active group timesharing is loaded, alkaline-earth metal has better facilitation than alkali metal；From implementation
The test result of example 1 and comparative example 2 can be seen that when using identical alkali or alkaline earth metal promotor, load your gold
Belonging to atomic ratio base metal atom has higher catalytic activity；From the survey of comparative example 1, comparative example 2 and comparative example 3, comparative example 4
Test result can be seen that when undoping alkali or alkaline earth metal promotor, the catalytic of the atom level site catalysts
It can not show a candle to the atom level site catalysts of alkali or alkaline earth metal promotion, therefore alkali or alkaline earth metal is mixed
It is miscellaneous, there is key effect to the degradation rate of VOCs under normal temperature and pressure for improving the catalyst.
Claims (5)
1. a kind of preparation method of load type nitrogen oxygen codope porous carbon atom level site catalysts, it is characterised in that including
Following steps:
(1) nitrogen oxygen codope porous carbon support is prepared, comprising the following steps:
The first step is successively 3%~5% with mass percent using grinder by 10~100g soybean slag grind into powder
HCl solution and distilled water are washed, and impurity and remaining hydrochloric acid in soy meal are removed, soybean ground-slag after then filtering
End is placed in 60~100 DEG C of baking ovens dry 1~4h, finally in a vacuum furnace with 200~400 DEG C of temperature in N2It is carbonized in atmosphere
Obtain soy meal within 1~3 hour；
The soy meal is immersed activation 12 in the KOH solution of 3~10mol/L~for 24 hours, makes soy meal and KOH matter by second step
Amount is subsequently placed in 40~100 DEG C of baking ovens dry 12~for 24 hours than being 2:1~4:1, in N in tube furnace after taking-up2Under atmosphere
It is carbonized, the control of tube furnace heating rate is warming up to 600~900 DEG C in 2~5 DEG C/min when carbonization, keeps 2~4h；
Third step, the powder after second step is carbonized naturally cool to 15~40 DEG C, impregnate 12 with the dilute acid soln of 1~3mol/L
~for 24 hours, and the powder after guaranteeing carbonization can be submerged by dilute acid soln completely, then it is washed with distilled water to PH=7, and in 60~
Dry 8 in 150 DEG C of baking ovens~for 24 hours, nitrogen oxygen codope porous carbon is obtained as carrier；
(2) carrying transition metal active component and alkali or alkaline earth metal promotor, comprising the following steps:
The first step weighs the porous carbon dust of 5~50g nitrogen oxygen codope in 50~500ml distilled water, 0.5~1h of ultrasonic disperse,
Form the first dispersion liquid；
The salt of transition metal or acid solution are added drop-wise in first dispersion liquid, are stirred evenly, obtained with glass bar by second step
To the first mixed liquor；Then alkali metal salt soln or alkaline-earth metal salt solution are added drop-wise in first mixed liquor, are shaken up
After obtain the second mixed liquor, make mass ratio 1:10~1 of transition metal and nitrogen oxygen codope porous carbon in the second mixed liquor:
104, the mass ratio of alkali or alkaline earth metal and nitrogen oxygen codope porous carbon is 1:25~1:104；
The second mixed liquor 0.5~3h of ultrasound is made transition metal and alkali or alkaline earth metal uniform load by third step
On nitrogen oxygen codope porous carbon support, after ultrasound, 10~30ml of sodium borohydride solution of 0.1~0.5mol/L is added, is formed
Third mixed liquor, and be vigorously stirred, until not generating H2, go back the metal ion being supported on nitrogen oxygen codope porous carbon
Then third mixed liquor is placed in 60~80 DEG C of oil bath pans by original, adjust pH to 6~9 with sodium carbonate liquor under stiring, add
2~4h of heat, until moisture is all evaporated to obtain sediment；
The sediment is washed with distilled water suction filtration 3~4 times by the 4th step, it is placed in 60~150 DEG C of baking ovens dry 8~
12h finally calcines 2~6h in the muffle furnace that temperature is 300~500 DEG C, obtains load type nitrogen oxygen codope after natural cooling
Porous carbon atom level site catalysts.
2. the preparation side of load type nitrogen oxygen codope porous carbon atom level site catalysts according to claim 1
Method, it is characterised in that: the dilute acid soln is one of hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid or acetum.
3. the system of load type nitrogen oxygen codope porous carbon atom level site catalysts according to claim 1 or 2
Preparation Method, it is characterised in that: the salt or acid solution of the transition metal are H2PtCl6、PdSO4、HAuCl4、AgNO3、RuCl3、
Rh(NO3)3、OsCl3、H2IrCl6、FeCl3、Co(NO3)2、Ni(NO3)2、Cu(NO3)2One or both of.
4. the preparation side of load type nitrogen oxygen codope porous carbon atom level site catalysts according to claim 3
Method, it is characterised in that: the alkali metal salt soln is that the nitrate solution, sulfate liquor or carbonate of alkali metal are molten
Liquid.
5. the preparation side of load type nitrogen oxygen codope porous carbon atom level site catalysts according to claim 3
Method, it is characterised in that: the alkaline-earth metal salt solution is the nitrate solution of alkaline-earth metal.
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| CN113699554A (en) * | 2021-09-17 | 2021-11-26 | 中国矿业大学 | Preparation method and application of rare earth metal and transition metal co-doped carbon-based material |
| CN115178285A (en) * | 2022-06-16 | 2022-10-14 | 佳化化学科技发展（上海）有限公司 | Catalyst for isomerizing glucose into fructose and preparation method thereof |
| CN115178285B (en) * | 2022-06-16 | 2024-03-08 | 佳化化学科技发展（上海）有限公司 | Catalyst for isomerising glucose into fructose and preparation method thereof |
| CN115155647A (en) * | 2022-08-25 | 2022-10-11 | 天津大学 | Preparation method and application of bimetal monoatomic supported BCN aerogel catalyst |
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