CN107774292A - A kind of preparation method of oxygen doping boron nitride catalyst carrier carried metal - Google Patents
A kind of preparation method of oxygen doping boron nitride catalyst carrier carried metal Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 104
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 33
- 239000002184 metal Substances 0.000 title claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 31
- 239000001301 oxygen Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- 229910052582 BN Inorganic materials 0.000 title claims abstract description 18
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 239000000969 carrier Substances 0.000 claims abstract description 25
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 18
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 13
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 230000033228 biological regulation Effects 0.000 claims abstract description 9
- 229910000765 intermetallic Inorganic materials 0.000 claims abstract description 7
- 150000002739 metals Chemical class 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 21
- 238000005554 pickling Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 8
- 239000004327 boric acid Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 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
- 238000010792 warming Methods 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-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
- 238000003828 vacuum filtration Methods 0.000 claims description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 5
- 229910052796 boron Inorganic materials 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000000320 mechanical mixture Substances 0.000 claims description 3
- 150000007522 mineralic acids Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000003993 interaction Effects 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 37
- 239000003643 water by type Substances 0.000 description 15
- 238000006555 catalytic reaction Methods 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 11
- 238000002835 absorbance Methods 0.000 description 10
- 238000004847 absorption spectroscopy Methods 0.000 description 10
- 230000008859 change Effects 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000012265 solid product Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000003837 high-temperature calcination Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009776 industrial production Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229960003638 dopamine Drugs 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000001458 anti-acid effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 235000006708 antioxidants Nutrition 0.000 description 1
- 150000001641 boron group compounds Chemical class 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation method of oxygen doping boron nitride catalyst carrier carried metal, including prepare d BN catalyst carriers；Deionized water is added, stirring, adds metallic compound；Ammoniacal liquor regulation pH, stirring is added dropwise；Filtering, washing；Product is re-dispersed into deionized water, stirring；It is slowly added to NaBH4Solution, and be stirred continuously；Filtering, washing, dry, that is, obtain d BN catalyst carrier carried metals.The d BN novel catalyst carriers that the present invention synthesizes have excellent heat endurance and chemical stability, O is entrained in BN lattices and C=O groups, part instead of N positions, so as to enhance the interaction of metal and carrier, substantially prolongs the service life cycle of catalyst.
Description
Technical field
The present invention relates to catalyst carrier material preparing technical field, more particularly to a kind of oxygen doping boron nitride (d-BN) to urge
The preparation method of agent carrier to load metal.
Background technology
Hexagonal boron nitride (h-BN) is a kind of important boron group compound, is hexagonal crystal system, and it has the layer of similar graphite
Shape structure, therefore also commonly known as " white graphite ".B-N is spaced in the h-BN of individual layer is arranged as plane hexagonal cyclic structure,
And the B-N keys in layer are with sp2The mode of hydridization covalent bond is combined together, and is combined with Van der Waals force between layers,
So every layer of h-BN structure is relatively stable, and it is relatively easy to peel off between layers.It is excellent because h-BN has unique structure
Mechanical strength, good heat endurance, anti-oxidant, acid and alkali-resistance and chemical inertness, make it in catalysis, aviation, ceramics, photic
There is great development prospect in the field such as luminous.
2005, Wu et al. was prepared for the h-BN catalyst of a series of Pt-Sn loads using infusion process, to crotonaldehyde
Selective hydrogenation shows good catalytic effect.Hereafter, using BN as catalyst carrier research and development work just present by
The trend that year rises, has become one of study hotspot of catalytic field.
H-BN is as catalyst carrier, and in the application process of reality, the cyclical stability of catalyst is often poor, repeatedly
Substantially reduced using rear catalytic activity.Recently, researcher utilizes theoretical modeling means, it was demonstrated that between perfect h-BN and metal
Interaction it is very weak so that the metallic particles for loading to h-BN carrier surfaces is very easy to come off, so as to result in catalysis live
The reduction of property.Therefore, the interaction between metal and h-BN, stabilization of the lifting metal in h-BN carrier surfaces how are strengthened
Property, be extend BN base catalyst service life cycle key.
At present, improving the method for the cyclical stability of BN base catalyst mainly has surface modification and surface modification etc..Wherein,
Surface modification is that there is highly viscous organic matter to be attached to h-BN surfaces dopamine etc., then makes metal particle deposition in DOPA
On amine, metallic is improved in the steady of h-BN carrier surfaces using the strong interaction between the organic matters such as metal and dopamine
It is qualitative.However, this method technique using organic matter modification h-BN is complex, it is unfavorable for industrialization large-scale production, limit
The actual use of this method is made.Surface modifying method is then to activate h-BN using strong acid, highly basic or oxidizing species, is made
It has the functional groups such as-OH or-COOH, using strong suction-operated of these functional groups to metal come stable metal particle, so that
Lift the cyclical stability of catalyst.But the activation process of this method is difficult to accurately control, and activation degree and h-BN bases
The defects of material itself, degree had compared with Important Relations, same unfavorable industrial production.
The content of the invention
In view of this, the embodiment provides a kind of oxygen doping BN catalyst carrier carried metals simple and easy to control
Preparation method, prepared catalyst carrier has excellent heat endurance and chemical stability, and the oxygen adulterated in carrier is former
Son can significantly increase the interaction of carrier and metal, greatly improve the cyclical stability of catalyst.
A kind of preparation method of oxygen doping boron nitride catalyst carrier carried metal of embodiments of the invention offer, including with
Lower step：
S1. d-BN catalyst carriers are prepared；
S2. the d-BN catalyst carriers of step S1 preparations are weighed, deionized water is added, stirring, adds metallic compound；
S3. ammoniacal liquor regulation pH, stirring is added dropwise；
S4. filter, wash；
S5. the step S4 products for washing to obtain are re-dispersed into deionized water, stirred；
S6. it is slowly added to NaBH4Solution, and be stirred continuously；
S7. filter, wash, dry, that is, obtain d-BN catalyst carrier carried metals.
Further, in the step S1, the specific method for preparing d-BN catalyst carriers is：
S1.1. melamine is sintered, natural cooling, obtains C3N4Intermediate；
S1.2. using boric acid as boron source and oxygen source, the C that is obtained with step S1.13N4It is for nitrogen source, the two mechanical mixture is uniform
Obtain predecessor；
S1.3. predecessor step S1.2 obtained is in N2Sintered under atmosphere, natural cooling, obtain material previously treated；
S1.4. by step S1.3 material previously treated pickling, filtering, washing；
S1.5. obtained product drying will be washed, be fully ground；
S1.6. the product sinters after step S1.5 is fully ground, natural cooling, that is, d-BN catalyst carriers are obtained.
Further, in the step S1.1, melamine is warming up to 400 DEG C~600 with 1~10 DEG C/min heating rate
DEG C, and sinter 2~4h at 400~600 DEG C.
Further, in the step S1.2, boric acid and C3N4Mol ratio between 16: 1~2: 1.
Further, in the step S1.3, predecessor is in N2It is warming up under atmosphere with 1~10 DEG C/min heating rate
800~1200 DEG C, and sinter 4~8h at 800~1200 DEG C.
Further, in the step S1.4, the acid of pickling is inorganic acid, and the acid of pickling is in hydrochloric acid, nitric acid and sulfuric acid
One kind, the sour concentration of aqueous solution of pickling is 1~20wt%；Washing is qualitative using multilayer during vacuum filtration using vacuum filtration
Filter paper filters；The pH value for being washed to cleaning solution is equal to 7.
Further, in the step S1.5, drying temperature is 65 DEG C, and drying time is 4~6h.
Further, in the step S1.6, the product after step S1.5 is fully ground is with 1~10 DEG C/min heating speed
Rate is warming up to 400~600 DEG C, and sinters 0.5~2h at 400~600 DEG C.
Further, the oxygen content scope adulterated in the d-BN catalyst carriers is 1.0~20.0at%.
Further, the metallic compound is one kind in gold chloride, copper chloride, iron chloride, chlorine palladium acid and silver nitrate.
Compared with prior art, the invention has the advantages that：Method is novel, and preparation technology is simple, synthesis temperature
It is low, can be inexpensively easy compared with oxygen doping type BN carrier of the preparation under temperate condition with high-specific surface area, abundant avtive spot, raw material
, it is adapted to large-scale industrial production and application, and the oxygen doping BN catalyst carriers synthesized have excellent heat endurance
And chemical stability；The present invention uses two-step method, and melamine high-temperature calcination is obtained into the C with two-dimension plane structure3N4It is middle
Body, using boric acid as boron source and oxygen source, with C3N4It is for nitrogen source and growth templates, both ground and mixeds are uniform, in N2It is high under atmosphere
Temperature calcining so that O atom is entrained in BN lattices and C=O groups during high-temperature calcination, partly instead of N positions, from
And the interaction of metal and carrier is enhanced, after active metal is carried on into the carrier, the cycle life of catalyst has larger
Lifting, catalytic activity be also significantly better than at present reported for work other similar to catalyst system and catalyzing, have stronger some commercial potential.
Brief description of the drawings
Fig. 1 is an a kind of flow chart of the preparation method of oxygen doping boron nitride catalyst carrier carried metal of the present invention.
Fig. 2 is the XRD of d-BN catalyst carriers in one embodiment of the invention.
Fig. 3 is the SEM figures of d-BN catalyst carriers in one embodiment of the invention.
Fig. 4 is the UV-Vis collection of illustrative plates that the present invention prepares CuNPs/d-BN catalysts reduction 4-NP.
Fig. 5 is the recycling conversion ratio figure that the present invention prepares CuNPs/d-BN catalysts reduction 4-NP.
Fig. 6 is CuNPs/h-BN catalysts reduction 4-NP UV-Vis collection of illustrative plates.
Fig. 7 is CuNPs/h-BN catalysts reduction 4-NP recycling conversion ratio figure.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is further described.
Fig. 1 is refer to, the embodiment provides a kind of system of oxygen doping boron nitride catalyst carrier carried metal
Preparation Method, comprise the following steps：
S1. d-BN catalyst carriers are prepared；
Specially：
S1.1. melamine is sintered, in one embodiment, melamine is heated up with 1~10 DEG C/min heating rate
2~4h is sintered to 400 DEG C~600 DEG C, and at 400~600 DEG C, natural cooling, obtains yellow solid C3N4Intermediate；
S1.2. using boric acid as boron source and oxygen source, the C that is obtained with step S1.13N4For nitrogen source, boric acid and C3N4Mol ratio
Between 16: 1~2: 1, the two mechanical mixture is uniformly obtained into faint yellow solid mixture, i.e. predecessor；
S1.3. predecessor step S1.2 obtained is in N2Sintered under atmosphere, in one embodiment, predecessor is in N2Atmosphere
Under with 1~10 DEG C/min heating rate be warming up to 800~1200 DEG C, and 4~8h are sintered at 800~1200 DEG C, natural cooling,
Obtain material previously treated；
S1.4. by step S1.3 material previously treated pickling, filtering, washing；
The acid of pickling is inorganic acid, and the acid of pickling is preferably one kind in hydrochloric acid, nitric acid and sulfuric acid, pickling it is sour water-soluble
Liquid concentration is 1~20wt%；Washing is filtered during vacuum filtration using vacuum filtration using multilayer qualitative filter paper；It is washed to washing
The pH value of liquid is equal to 7；
S1.5. obtained product drying will be washed, drying temperature is preferably 65 DEG C, and drying time is 4~6h, is fully ground
Mill, obtains white solid product；
S1.6. after step S1.5 is fully ground white solid product sintering, in one embodiment, with 1~10 DEG C/
Min heating rate is warming up to 400~600 DEG C, and sinters 0.5~2h at 400~600 DEG C, natural cooling, that is, obtains d-BN and urges
Agent carrier (as shown in Figures 2 and 3), the oxygen content scope adulterated in d-BN catalyst carriers is 1.0~20.0at%.
S2. the d-BN catalyst carriers of step S1 preparations are weighed, deionized water is added, stirring, adds metallic compound,
In one embodiment, metallic compound is one kind in gold chloride, copper chloride, iron chloride, chlorine palladium acid and silver nitrate；
S3. ammoniacal liquor regulation pH is added dropwise, stirs 12h；
S4. filter, wash；
S5. the step S4 products for washing to obtain are re-dispersed into deionized water, stirred；
S6. 4mL NaBH are slowly added to4Solution, and it is stirred continuously 1h；
S7. filter, wash, in one embodiment, be washed with deionized 5 times, dry, in one embodiment, at 65 DEG C
4~6h of lower drying, that is, obtain d-BN catalyst carrier carried metals.
Application examples 1
D-BN catalyst carriers are prepared according to the inventive method, and AuNPs/d-BN catalyst is prepared by the inventive method,
Its preparation method is：
D-BN powder 0.196g is weighed in beaker, 40mL deionized waters is added, is stirred continuously down, is added certain density
Gold chloride, ammoniacal liquor regulation pH is added dropwise, stirs 12h, filters, washing, product is re-dispersed into deionized water, is slowly added to
4mL NaBH4Solution is simultaneously stirred continuously 1h, filtering, is washed with deionized 5 times, and gained purple solid product is dried at 65 DEG C
4~6h, AuNPs/d-BN catalyst is obtained, Au load capacity is 0.5~2.5wt%.
Catalytic performance test：
10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs the above-mentioned AuNPs/d- of 5mg
BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, fast transfer is to anti-
Answer and start catalytic reaction in device, the liquid in reactor is carried out every 30s using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
Monitoring, detects the absorbance change at 400nm, conversion ratio is calculated as the following formula：
In formula：η is conversion ratio, C04-NP concentration, C during to react initialtFor the concentration of 4-NP after reaction t.
After reacting 3min, 4-NP conversion ratio reaches 100%.
After AuNPs/d-BN catalyst recycles 6 times, still in 3min 4-NP conversion ratio can be caused to reach 98.5%.
Comparative run：10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs 5mg
AuNPs/h-BN catalyst is placed in reactor, and d-BN and h-BN atomicity percentage composition and specific surface area contrast are shown in Table 1, fill
Divide stirring catalyst is uniformly dispersed, measure 5mL NaBH4Solution, fast transfer start catalytic reaction into reactor.
The d-BN of table 1 and h-BN atomicity percentage composition and specific surface area
| Sample | B/at% | C/at% | N/at% | O/at% | Specific surface area |
| h-BN | 44.25 | 19.04 | 35.36 | 3.15 | 16 |
| d-BN | 44.4 | 3.0 | 36.9 | 15.7 | 216 |
Detected using ultraviolet-visible absorption spectroscopy instrument (UV-Vis) every 30s to being monitored to the liquid in reactor
Absorbance change at 400nm.
12min is reacted, 4-NP conversion ratio reaches 90%.
After AuNPs/h-BN catalyst recycles 6 times, during 12min, 4-NP conversion ratio is reduced to 50.3%.
Application examples 2
D-BN catalyst carriers are prepared according to the inventive method, and CuNPs/d-BN catalyst is prepared by the inventive method,
Its preparation method is：
D-BN powder 0.196g is weighed in beaker, 40mL deionized waters is added, is stirred continuously down, is added certain density
Copper chloride, ammoniacal liquor regulation pH is added dropwise, stirs 12h, filters, washing, product is re-dispersed into deionized water, is slowly added to
4mL NaBH4Solution is simultaneously stirred continuously 1h, filtering, is washed with deionized 5 times, and gained brown solid is dried at 65 DEG C
4~6h, CuNPs/d-BN catalyst is obtained, Cu load capacity is 0.5~2.5wt%.
Catalytic performance test：
10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs the above-mentioned CuNPs/d- of 5mg
BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, fast transfer is to anti-
Answer and start catalytic reaction in device, the liquid in reactor is carried out every 1min using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
Monitoring, detects the absorbance change (as shown in Figure 4) at 400nm, conversion ratio is calculated as the following formula：
In formula：η is conversion ratio, C04-NP concentration, C during to react initialtFor the concentration of 4-NP after reaction t.
After reacting 5min, 4-NP conversion ratio reaches 99.5%.
After CuNPs/d-BN catalyst recycles 6 times, still in 5min 4-NP conversion ratio can be caused to reach 98.5%
(as shown in Figure 5).
Comparative run：10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs 5mg
CuNPs/h-BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, quickly
It is transferred in reactor and starts catalytic reaction, using ultraviolet-visible absorption spectroscopy instrument (UV-Vis) every 2min in reactor
Liquid is monitored, and detects the absorbance change (as shown in Figure 6) at 400nm.
11min is reacted, 4-NP conversion ratio reaches 95.45%.
After CuNPs/h-BN catalyst recycles 6 times, during 11min, 4-NP conversion ratio is reduced to 48.3% (such as Fig. 7 institutes
Show).
Application examples 3
D-BN catalyst carriers are prepared according to the inventive method, and FeNPs/d-BN catalyst is prepared by the inventive method,
Its preparation method is：
D-BN powder 0.196g is weighed in beaker, 40mL deionized waters is added, is stirred continuously down, is added certain density
Iron chloride, ammoniacal liquor regulation pH is added dropwise, stirs 12h, filters, washing, product is re-dispersed into deionized water, is slowly added to
4mL NaBH4Solution is simultaneously stirred continuously 1h, filtering, is washed with deionized 5 times, and gained black solid product is dried at 65 DEG C
4~6h, FeNPs/d-BN catalyst is obtained, Fe load capacity is 0.5~2.5wt%.
Catalytic performance test：
10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs the above-mentioned FeNPs/d- of 5mg
BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, fast transfer is to anti-
Answer and start catalytic reaction in device, the liquid in reactor is carried out every 30s using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
Monitoring, detects the absorbance change at 400nm, conversion ratio is calculated as the following formula：
In formula：η is conversion ratio, C04-NP concentration, C during to react initialtFor the concentration of 4-NP after reaction t.
After reacting 4min, 4-NP conversion ratio reaches 99.5%.
After FeNPs/d-BN catalyst recycles 6 times, still in 4min 4-NP conversion ratio can be caused to reach 97.8%.
Comparative run：10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs 5mg
CuNPs/h-BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, quickly
It is transferred in reactor and starts catalytic reaction, using ultraviolet-visible absorption spectroscopy instrument (UV-Vis) every 2min in reactor
Liquid is monitored, and detects the absorbance change at 400nm.
After reacting 15min, 4-NP conversion ratio reaches 93.4%.
After FeNPs/h-BN catalyst recycles 6 times, during 15min, 4-NP conversion ratio is reduced to 45.2%.
Application examples 4
D-BN catalyst carriers are prepared according to the inventive method, and PdNPs/d-BN catalyst is prepared by the inventive method,
Its preparation method is：
D-BN powder 0.196g is weighed in beaker, 40mL deionized waters is added, is stirred continuously down, is added certain density
Palladium bichloride, ammoniacal liquor regulation pH is added dropwise, stirs 12h, filters, washing, product is re-dispersed into deionized water, is slowly added to
4mL NaBH4Solution is simultaneously stirred continuously 1h, filtering, is washed with deionized 5 times, and gained gray solid product is dried at 65 DEG C
4~6h, PdNPs/d-BN catalyst is obtained, Pd load capacity is 0.5~2.5wt%.
Catalytic performance test：
10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs the above-mentioned PdNPs/d- of 5mg
BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, fast transfer is to anti-
Answer and start catalytic reaction in device, the liquid in reactor is carried out every 2min using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
Monitoring, detects the absorbance change at 400nm, conversion ratio is calculated as the following formula：
In formula：η is conversion ratio, C04-NP concentration, C during to react initialtFor the concentration of 4-NP after reaction t.
After reacting 10min, 4-NP conversion ratio reaches 98.7%.
After PdNPs/d-BN catalyst recycles 6 times, still in 10min 4-NP conversion ratio can be reached
98.5%.
Comparative run：10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs 5mg
PdNPs/h-BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, quickly
It is transferred in reactor and starts catalytic reaction, using ultraviolet-visible absorption spectroscopy instrument (UV-Vis) every 2min in reactor
Liquid is monitored, and detects the absorbance change at 400nm.
After reacting 25min, 4-NP conversion ratio reaches 92.3%.
After PdNPs/h-BN catalyst recycles 6 times, during 25min, 4-NP conversion ratio is reduced to 44.6%.
Application examples 5
D-BN catalyst carriers are prepared according to the inventive method, and AgNPs/d-BN catalyst is prepared by the inventive method,
Its preparation method is：
D-BN powder 0.196g is weighed in beaker, 40mL deionized waters is added, is stirred continuously down, is added certain density
Silver nitrate, ammoniacal liquor regulation pH is added dropwise, stirs 12h, filters, washing, product is re-dispersed into deionized water, is slowly added to
4mL NaBH4Solution is simultaneously stirred continuously 1h, filtering, is washed with deionized 5 times, and gained yellow solid product is dried at 65 DEG C
4~6h, AgNPs/d-BN catalyst is obtained, Ag load capacity is 0.5~2.5wt%.
Catalysis efficiency is evaluated：
10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs the above-mentioned AgNPs/d- of 5mg
BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, fast transfer is to anti-
Answer and start catalytic reaction in device, the liquid in reactor is carried out every 2min using ultraviolet-visible absorption spectroscopy instrument (UV-Vis)
Monitoring, detects the absorbance change at 400nm, conversion ratio is calculated as the following formula：
In formula：η is conversion ratio, C04-NP concentration, C during to react initialtFor the concentration of 4-NP after reaction t.
After reacting 10min, 4-NP conversion ratio reaches 98.7%.
After AgNPs/d-BN catalyst recycles 6 times, still in 10min 4-NP conversion ratio can be reached
98.5%.
Comparative run：10mL deionized waters are taken in reactor, the 4-NP that 0.5mL concentration is 5mM is added, weighs 5mg
AgNPs/h-BN catalyst is placed in reactor, and being sufficiently stirred makes catalyst be uniformly dispersed, and measures 5mL NaBH4Solution, quickly
It is transferred in reactor and starts catalytic reaction, using ultraviolet-visible absorption spectroscopy instrument (UV-Vis) every 2min in reactor
Liquid is monitored, and detects the absorbance change at 400nm.
After reacting 14min, 4-NP conversion ratio reaches 91.7%.
After AgNPs/h-BN catalyst recycles 6 times, during 14min, 4-NP conversion ratio is reduced to 44.8%.
The inventive method is novel, and preparation technology is simple, and synthesis temperature is low, can have Gao Bibiao compared with preparation under temperate condition
The oxygen doping type BN carriers of area, abundant avtive spot, raw material is cheap and easy to get, is adapted to large-scale industrial production and application, and
And the oxygen doping BN catalyst carriers of synthesis have excellent heat endurance and chemical stability；The present invention uses two-step method, will
Melamine high-temperature calcination obtains the C with two-dimension plane structure3N4Intermediate, using boric acid as boron source and oxygen source, with C3N4For nitrogen
Source and growth templates, both ground and mixeds are uniform, in N2Under atmosphere, high-temperature calcination so that process of the O atom in high-temperature calcination
In be entrained in BN lattices and C=O groups, partly instead of N positions, enhance the interaction of metal and carrier, by activity
After the carrier, the cycle life of catalyst has a distinct increment Metal Supported, and catalytic activity is also significantly better than what is reported for work at present
Other have stronger some commercial potential similar to catalyst system and catalyzing.
In the case where not conflicting, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (10)
1. a kind of preparation method of oxygen doping boron nitride catalyst carrier carried metal, it is characterised in that comprise the following steps：
S1. d-BN catalyst carriers are prepared；
S2. the d-BN catalyst carriers of step S1 preparations are weighed, deionized water is added, stirring, adds metallic compound；
S3. ammoniacal liquor regulation pH, stirring is added dropwise；
S4. filter, wash；
S5. the step S4 products for washing to obtain are re-dispersed into deionized water, stirred；
S6. it is slowly added to NaBH4Solution, and be stirred continuously；
S7. filter, wash, dry, that is, obtain d-BN catalyst carrier carried metals.
2. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 1, it is characterised in that
In the step S1, the specific method for preparing d-BN catalyst carriers is：
S1.1. melamine is sintered, natural cooling, obtains C3N4Intermediate；
S1.2. using boric acid as boron source and oxygen source, the C that is obtained with step S1.13N4For nitrogen source, the two mechanical mixture is uniformly obtained
Predecessor；
S1.3. predecessor step S1.2 obtained is in N2Sintered under atmosphere, natural cooling, obtain material previously treated；
S1.4. by step S1.3 material previously treated pickling, filtering, washing；
S1.5. obtained product drying will be washed, be fully ground；
S1.6. the product sinters after step S1.5 is fully ground, natural cooling, that is, d-BN catalyst carriers are obtained.
3. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
In the step S1.1, melamine is warming up to 400 DEG C~600 DEG C with 1~10 DEG C/min heating rate, and 400~600
DEG C sintering 2~4h.
4. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
In the step S1.2, boric acid and C3N4Mol ratio 16:1~2:Between 1.
5. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
In the step S1.3, predecessor is in N2Under atmosphere 800~1200 DEG C are warming up to 1~10 DEG C/min heating rate, and
800~1200 DEG C of 4~8h of sintering.
6. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
In the step S1.4, the acid of pickling is inorganic acid, and the acid of pickling is one kind in hydrochloric acid, nitric acid and sulfuric acid, pickling it is sour
Concentration of aqueous solution is 1~20wt%；Washing is filtered during vacuum filtration using vacuum filtration using multilayer qualitative filter paper；It is washed to
The pH value of cleaning solution is equal to 7.
7. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
In the step S1.5, drying temperature is 65 DEG C, and drying time is 4~6h.
8. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
In the step S1.6, product after step S1.5 is fully ground is warming up to 400 with 1~10 DEG C/min heating rate~
600 DEG C, and sinter 0.5~2h at 400~600 DEG C.
9. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 2, it is characterised in that
The oxygen content scope adulterated in the d-BN catalyst carriers is 1.0~20.0at%.
10. the preparation method of oxygen doping boron nitride catalyst carrier carried metal according to claim 1, its feature exist
In the metallic compound is one kind in gold chloride, copper chloride, iron chloride, chlorine palladium acid and silver nitrate.
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| CN103111245A (en) * | 2013-03-20 | 2013-05-22 | 福州大学 | Method for preparing silver-nanoparticle-loaded multilayer graphite-phase boron nitride colloid |
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| CN106179443A (en) * | 2016-07-05 | 2016-12-07 | 汕头大学 | The bimetallic catalyst with core-casing structure of a kind of hexagonal boron nitride nanosheet load and preparation and application thereof |
| CN106496063A (en) * | 2016-10-21 | 2017-03-15 | 福州大学 | A kind of method for preparing hydrodiazo benzene-like compounds |
| CN106744736A (en) * | 2016-12-26 | 2017-05-31 | 湖北第二师范学院 | A kind of synthetic method of the active porous boron nitride nanosheet for water process |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103111245A (en) * | 2013-03-20 | 2013-05-22 | 福州大学 | Method for preparing silver-nanoparticle-loaded multilayer graphite-phase boron nitride colloid |
| CN104889382A (en) * | 2015-04-27 | 2015-09-09 | 中国科学院深圳先进技术研究院 | Preparation method of deposition nano-silver particulate composite materials of hexagonal boron nitride nanosheet |
| CN106179443A (en) * | 2016-07-05 | 2016-12-07 | 汕头大学 | The bimetallic catalyst with core-casing structure of a kind of hexagonal boron nitride nanosheet load and preparation and application thereof |
| CN106496063A (en) * | 2016-10-21 | 2017-03-15 | 福州大学 | A kind of method for preparing hydrodiazo benzene-like compounds |
| CN106744736A (en) * | 2016-12-26 | 2017-05-31 | 湖北第二师范学院 | A kind of synthetic method of the active porous boron nitride nanosheet for water process |
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