CN114984995B - Preparation method for converting lignin into various hetero-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction - Google Patents
Preparation method for converting lignin into various hetero-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 117
- 239000002131 composite material Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 title claims abstract description 45
- 229910021392 nanocarbon Inorganic materials 0.000 title claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 36
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 150000007524 organic acids Chemical class 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 28
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000001354 calcination Methods 0.000 claims abstract description 24
- 238000001914 filtration Methods 0.000 claims abstract description 23
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000005406 washing Methods 0.000 claims abstract description 17
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 16
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000011574 phosphorus Substances 0.000 claims abstract description 16
- 229910052796 boron Inorganic materials 0.000 claims abstract description 15
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 14
- 239000011593 sulfur Substances 0.000 claims abstract description 14
- 238000004108 freeze drying Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 12
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 23
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 238000001291 vacuum drying Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 11
- 238000010992 reflux Methods 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 10
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 150000001299 aldehydes Chemical class 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- FFEARJCKVFRZRR-BYPYZUCNSA-N L-methionine Chemical compound CSCC[C@H](N)C(O)=O FFEARJCKVFRZRR-BYPYZUCNSA-N 0.000 claims description 7
- 229930182817 methionine Natural products 0.000 claims description 7
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 125000004429 atom Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 235000002949 phytic acid Nutrition 0.000 claims description 6
- 239000000467 phytic acid Substances 0.000 claims description 6
- 229940068041 phytic acid Drugs 0.000 claims description 6
- 239000004327 boric acid Substances 0.000 claims description 5
- 239000005416 organic matter Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 3
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 3
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 3
- 235000018417 cysteine Nutrition 0.000 claims description 3
- 229960003067 cystine Drugs 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- ZZYXNRREDYWPLN-UHFFFAOYSA-N pyridine-2,3-diamine Chemical compound NC1=CC=CN=C1N ZZYXNRREDYWPLN-UHFFFAOYSA-N 0.000 claims description 3
- AJSTXXYNEIHPMD-UHFFFAOYSA-N triethyl borate Chemical compound CCOB(OCC)OCC AJSTXXYNEIHPMD-UHFFFAOYSA-N 0.000 claims description 3
- WRECIMRULFAWHA-UHFFFAOYSA-N trimethyl borate Chemical compound COB(OC)OC WRECIMRULFAWHA-UHFFFAOYSA-N 0.000 claims description 3
- NHDIQVFFNDKAQU-UHFFFAOYSA-N tripropan-2-yl borate Chemical compound CC(C)OB(OC(C)C)OC(C)C NHDIQVFFNDKAQU-UHFFFAOYSA-N 0.000 claims description 3
- 125000003277 amino group Chemical group 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims 3
- LEVWYRKDKASIDU-QWWZWVQMSA-N D-cystine Chemical compound OC(=O)[C@H](N)CSSC[C@@H](N)C(O)=O LEVWYRKDKASIDU-QWWZWVQMSA-N 0.000 claims 1
- 239000000243 solution Substances 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 238000003756 stirring Methods 0.000 description 24
- 239000000463 material Substances 0.000 description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
- 239000001301 oxygen Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 7
- 239000003575 carbonaceous material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 229910052755 nonmetal Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 235000005985 organic acids Nutrition 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000006722 reduction reaction Methods 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- LQEQXNYQQIBNEM-UHFFFAOYSA-N ethynylphosphane Chemical compound PC#C LQEQXNYQQIBNEM-UHFFFAOYSA-N 0.000 description 3
- 238000003837 high-temperature calcination Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- LEVWYRKDKASIDU-IMJSIDKUSA-N L-cystine Chemical compound [O-]C(=O)[C@@H]([NH3+])CSSC[C@H]([NH3+])C([O-])=O LEVWYRKDKASIDU-IMJSIDKUSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 101150112420 lnpka gene Proteins 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- XFZRQAZGUOTJCS-UHFFFAOYSA-N phosphoric acid;1,3,5-triazine-2,4,6-triamine Chemical compound OP(O)(O)=O.NC1=NC(N)=NC(N)=N1 XFZRQAZGUOTJCS-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 206010017740 Gas poisoning Diseases 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- BFZUFHPKKNHSAG-UHFFFAOYSA-N [N].[P].[S] Chemical compound [N].[P].[S] BFZUFHPKKNHSAG-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- UBIJTWDKTYCPMQ-UHFFFAOYSA-N hexachlorophosphazene Chemical compound ClP1(Cl)=NP(Cl)(Cl)=NP(Cl)(Cl)=N1 UBIJTWDKTYCPMQ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229920005615 natural polymer Polymers 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
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- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- 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
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- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- 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
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- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
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- 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
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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Abstract
The invention discloses a preparation method of a nano carbon-based composite nonmetallic catalyst doped with multiple hetero atoms by converting lignin into various hetero atoms through surface interface reaction, which comprises the following steps: preparing amino-lignin; dissolving amino-lignin in deionized water, performing ultrasonic treatment, adding at least one of a phosphorus-containing organic acid solution, a boron-containing organic acid solution and a sulfur-containing organic acid solution, reacting for 2-4 hours at room temperature, filtering, washing for many times, adjusting the pH value to be neutral, and performing freeze drying to obtain a polyatomic doped amino-lignin product; calcining the multi-atom doped amino-lignin product at high temperature in nitrogen or argon atmosphere to obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts. The preparation condition is mild, the cost is low, and the formed nonmetallic composite catalyst has excellent cycle stability.
Description
Technical Field
The invention belongs to the technical field of biomass waste conversion and electrocatalysis, and relates to a preparation method of a nano carbon-based composite nonmetallic catalyst doped with multiple hetero atoms by converting lignin through surface-interface reaction.
Background
Lignin is the second most abundant natural polymer on earth and is also the only natural source of large-scale aromatic compounds in the biosphere consisting of about 30% organic carbon. Considering that most of waste lignin is burned or directly discarded, research on lignin recycling is continuously developed, and lignin can be used as an additive of engineering composite materials, degraded into micromolecular chemicals and converted into carbon materials to be applied to the field of energy.
Noble metals and their compounds for ORR and OER present problems in terms of selectivity, durability and sensitivity to gas poisoning, with potential environmental hazards and relatively limited resource limitations. Materials with the advantages of high selectivity, durability and environmental inertness are therefore continually being pursued as potential alternatives to the ORR and OER industry standards. On the basis of exploring the operation mechanism of the catalytic site, the carbon-based material is one of the main members of a nonmetallic catalyst, wherein hetero atoms (nitrogen, phosphorus, sulfur and the like) are doped to enable the carbon material to have better catalytic performance. The Chinese patent publication No. CN 112221527B discloses a N, S co-doped porous carbon coated carbon nanotube bifunctional oxygen electrode catalyst and a preparation method thereof, wherein sulfide is subjected to high-temperature pretreatment for doping sulfur element, a reaction solvent is hydrochloric acid, and the reaction process is in an acidic environment, so that the disadvantages of harsh synthesis conditions, moderate synthesis conditions and the like are caused, and the carbon material used is carbon nanotubes, so that the synthesis cost is high. The Chinese patent with publication number of CN111111637A discloses a boron doped non-metal catalyst, a preparation method and application thereof, and a boron doped carbon non-metal catalyst material is obtained by high-temperature calcination, wherein strong acid with strong oxidizing property such as nitric acid is needed to be used in the process of treating carbon materials, so that synthesis conditions are harsh, potential safety hazards are easily caused, and a reaction system in the patent is mainly an organic system solution, so that the cost is high and the stability is poor. The Chinese patent with the publication number of CN111717902B discloses a nitrogen-phosphorus-sulfur co-doped porous carbon-loaded metal phosphide nanocomposite, a preparation method and application thereof, wherein a phosphorus source and a sulfur source used are hexachlorocyclotriphosphazene and 4, 4-dihydroxydiphenyl sulfone, a system used in the reaction is an organic solution such as methanol, and a finally generated product is the metal phosphide nanocomposite, and compared with a metal material of a comparison patent, the nonmetal material has the characteristics of low cost, less environmental pollution and the like. The invention discloses an electronegative heteroatom-transition metal co-doped carbon-based non-noble metal electrocatalyst and a preparation method thereof, wherein the electronegative heteroatom-transition metal co-doped carbon-based non-noble metal electrocatalyst is obtained by mixing a carbon source, a phosphorus source, a nitrogen source, a sulfur source and transition metal salt, performing hydrothermal high-temperature reaction, and then performing high-temperature calcination in nitrogen atmosphere.
Disclosure of Invention
The embodiment of the invention aims to provide a preparation method for converting lignin into various hetero-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, so as to solve the problems of severe and milder preparation conditions, high cost, large environmental pollution and poor stability of catalytic materials in the existing catalytic field.
The technical scheme adopted by the embodiment of the invention is as follows: the preparation method for converting lignin into various hetero-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction is carried out according to the following steps:
s1, preparing amino-lignin;
s2, dissolving amino-lignin in deionized water, performing ultrasonic treatment, adding at least one of a phosphorus-containing organic acid solution, a boron-containing organic acid solution and a sulfur-containing organic acid solution, reacting for 2-4 hours at room temperature, filtering, washing for many times, adjusting the pH value to be neutral, and performing freeze drying to obtain a polyatomic doped amino-lignin product;
and S3, calcining the multi-atom doped amino-lignin product at high temperature in nitrogen or argon atmosphere to obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Further, the phosphorus-containing organic acids of step S2 include, but are not limited to, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, phytic acid, the sulfur-containing organic acids include, but are not limited to, cystine, cysteine, methionine, melamine phosphate, and the boron-containing organic acids include, but are not limited to, terephthal-boric acid, trimethyl borate, triethyl borate, triisopropyl borate.
Further, the calcination temperature in the step S3 is 800-1200 ℃ and the calcination time is 1-5 hours.
Further, in the step S2, when 1g of amino-lignin is added, the total amount of the added phosphoric acid-containing organic acid solution, the sulfur-containing organic acid solution and the boron-containing organic acid solution is 1-20 ml, and the mass concentration of the added phosphoric acid-containing organic acid solution, the sulfur-containing organic acid solution and the boron-containing organic acid solution is 10-70 wt%.
Further, the specific process of step S1 is as follows:
mixing the lignin after acid washing with amino-containing organic matters and aldehyde organic matters, adjusting the pH value to 9-11, heating, adding isopropanol, filtering, separating and vacuum drying to obtain the amino-lignin.
Further, amino-containing organics include, but are not limited to, tetraethylenepentamine, ethylenediamine, m-phenylenediamine, 2, 3-diaminopyridine.
Further, the aldehyde organics include, but are not limited to, formaldehyde, glyoxal.
Further, the mass ratio of lignin to amino-containing organic matter is 1: 0.1-1: 5, a step of;
the heating in the step S1 is divided into two steps, wherein the heating temperature in the first step is 60-90 ℃, the heating temperature in the second step is 100-120 ℃, and the reflux is carried out for 3-6 hours after the heating in the second step; the drying temperature of vacuum drying is 40-60deg.C, and the drying time is 8-12 hr.
Further, in the step S1, 1g of lignin is added, and 0.1-30 mmol of amino-containing organic matter and 10-20 mmol of aldehyde organic matter are correspondingly added.
The embodiment of the invention has the beneficial effects that:
1. the catalytic material uses lignin with lower cost as a carbon source, realizes doping of various heteroatoms through complexation reaction, breaks through the limitation of regulating and controlling the performance of the carbon-based catalyst in the currently commonly adopted single-atom doping mode, provides an effective realization way of renewable energy sources and a value-added scheme of biomass waste, and is suitable for quantitative preparation and industrial production;
2. the lignin is modified and doped through a surface-interface chemical reaction, a plurality of hetero atoms are introduced, nonmetal nano particles with catalytic activity are generated in the nano carbon base doped with the plurality of hetero atoms, biomass waste lignin is converted into a plurality of nano carbon base composite nonmetal catalysts doped with hetero atoms, the preparation condition is mild, the cost is low, the formed nonmetal composite catalyst has excellent circulation stability, the barrier of the harsh and even dangerous reaction/activation condition required in the process of realizing multiple activation doping at present is overcome, and the problems of harsh and non-mild preparation conditions, high cost, large environmental pollution and poor stability of catalytic materials in the existing catalytic field are solved;
3. the prepared multiple hetero-atom doped nano carbon-based composite nonmetallic catalysts (nonmetallic nano particle modified doped carbon-based composite catalysts) have double promotion effects on electrocatalytic oxygen evolution activity and oxygen reduction activity;
4. the used raw materials greatly reduce the pollution to the environment and the harm to human bodies in the production and treatment process.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic representation of the synthesis of a final product from high temperature pyrolysis of a complex product of an embodiment of the present invention.
Fig. 2 is a scanning electron microscope image of a carbon-based composite nonmetallic nanoparticle (LNPA).
Fig. 3 is an x-ray photoelectron spectrum of a carbon-based composite nonmetallic nanoparticle (LNPA).
FIG. 4 is a Fourier infrared spectrometer comparison of lignin, amino-lignin and products obtained by freeze-drying after complexation of amino-lignin with phytic acid (LNP).
Fig. 5 (a) is an X-ray diffraction pattern of carbon nitride and carbon phosphide in the carbon-based composite nonmetallic nanoparticle.
Fig. 5 (b) is a transmission electron microscope image of carbon nitride in the carbon-based composite nonmetallic nanoparticle.
Fig. 5 (c) is a transmission electron microscope image of the carbon phosphide in the carbon-based composite nonmetallic nanoparticle.
FIG. 6 shows the atomic concentrations of nitrogen and phosphorus doped in examples 2 to 4.
FIG. 7 is a Tafil diagram showing the oxygen reduction reaction region in examples 2 to 4.
FIG. 8 is a Tafil diagram of the catalytic oxygen evolution reaction zone of examples 2-4.
FIG. 9 is a time-current diagram of example 3 at 0.4V vs. standard hydrogen evolution potential of 0.1M potassium hydroxide at 800 rpm, showing the crossover effect of Pt/C and the products of examples 2-4 at 0.4V vs. standard hydrogen evolution potential.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and completely with reference to the accompanying drawings, in which it is apparent that the embodiments described are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, mixing the lignin subjected to acid washing with amino-containing organic matters and aldehyde organic matters, adjusting the pH value to 9-11, heating, adding isopropanol, filtering, separating and vacuum drying to obtain amino-lignin; the purpose of acid washing is to remove impurities in lignin and improve the purity of raw materials; the isopropanol is added to terminate the reaction so as to regulate the reaction progress;
s2, dissolving amino-lignin in deionized water and performing ultrasonic treatment, and then adding at least one of a phosphorus-containing organic acid solution, a boron-containing organic acid solution and a sulfur-containing organic acid solution, wherein the amino-lignin reacts with the phosphorus-containing organic acid solution, the boron-containing organic acid solution and/or the sulfur-containing organic acid solution for 2-4 hours at room temperature; boron, phosphorus and sulfur atoms are doped into lignin through complexation reaction between surface boundaries; then filtering and washing for many times, adjusting the pH value to be neutral, and freeze-drying to obtain a multi-atom doped amino-lignin product; the room temperature needs to be below 50 ℃, and if the room temperature exceeds 50 ℃, coordination can be affected;
and S3, calcining the multi-atom doped amino-lignin product in nitrogen or argon atmosphere at 800-1200 ℃ for 1-5 hours, wherein finally nitrogen, phosphorus and/or boron atoms can generate composite crystals of a nonmetallic nano structure in a carbon base to obtain various hetero-atom doped nano carbon base composite nonmetallic materials, as shown in figure 1.
In some embodiments, the amino-containing organics in step S1 include, but are not limited to, tetraethylenepentamine, ethylenediamine, metaphenylene diamine, 2, 3-diaminopyridine, and the like, with a lignin to amino-containing organics mass ratio of 1: 0.1-1: and 5, adjusting the content of the ammonia-containing organic matters to obtain the optimal doping content of the amino groups.
In some embodiments, the amino-containing organic matter is tetraethylenepentamine, and the optimal mass ratio of lignin to tetraethylenepentamine is 1:0.9.
in some embodiments, the alkaline solution required for adjusting the pH value in the step S1 includes, but is not limited to, sodium hydroxide and potassium hydroxide, and the concentration of the alkaline solution is between 0.1 mol/L and 0.5 mol/L.
In some embodiments, in step S1, the aldehyde organics include, but are not limited to, formaldehyde, glyoxal.
In some embodiments, the heating in step S1 is divided into two steps, the first heating temperature is 60-90 ℃, the second heating temperature is 100-120 ℃, and the reflux is performed for 3-6 hours after the second heating; the drying temperature of vacuum drying is 40-60deg.C, and the drying time is 8-12 hr.
In some embodiments, the phosphorus-containing organic acid of step S2 includes, but is not limited to, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid, phytic acid, and the like; sulfur-containing organic acids include, but are not limited to, cystine, cysteine, methionine, melamine phosphate, and the like; the boron-containing organic acids include, but are not limited to, terephthal-acid, trimethyl borate, triethyl borate, triisopropyl borate, and the like.
In some embodiments, when 1g of amino-lignin is added in step S2, the total amount of the added phosphoric acid-containing organic acid solution, sulfuric acid-containing organic acid solution and boric acid-containing organic acid solution is 1-20 ml, and the mass concentration of the added phosphoric acid-containing organic acid solution, sulfuric acid-containing organic acid solution and boric acid-containing organic acid solution is 10wt% -70 wt%.
Example 2
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then 5mmol of tetraethylenepentamine are added with stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 10; adding 15mmol of formaldehyde, heating to 85 ℃, and then further heating to 100 ℃ and refluxing for 4 hours; after isopropanol was added, the reaction was stopped; filtering and separating the product, washing the product with isopropanol, and vacuum drying the product for 12 hours at the temperature of 40 ℃ to obtain amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding 8 ml of phytic acid solution with the mass concentration of 50wt% and reacting for 3 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product for 2 hours under the atmosphere of 900 ℃ and nitrogen to obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts, namely LNPA-900. The doping atomic percentages in LNPA-900 are: 2.21% N, 2.89% P. In the Tafil curve of the oxygen reduction reaction zone, the slope of LNPA-900 was 41.3 mVdecade -1 As shown in fig. 7; in the Tafil curve of the oxygen evolution reaction zone, the slope of LNPA-900 was 236 mVdecade -1 As shown in fig. 8.
Example 3
The procedure of preparation before calcination was the same as in example 2, and calcination was carried out at 1000℃under nitrogen atmosphere for 2 hours to obtain various heteroatomic doped nanocarbon-based composite nonmetallic catalysts, denoted as LNPA-1000. The doping atomic percentages in LNPA-1000 are: 1.68% N, 2.19% P. In the Tafil curve of the oxygen reduction reaction zone, the slope of LNPA-1000 was 39.4 mVdecade -1 As shown in fig. 7; in the Tafil curve of the oxygen evolution reaction zone, the slope of LNPA-1000 is 125 mVdecade -1 As shown in fig. 8.
Example 4
The procedure of preparation before calcination was the same as in example 2, and calcination was carried out at 1100℃under nitrogen atmosphere for 2 hours to obtain various heteroatomic doped nanocarbon-based composite nonmetallic catalysts, denoted as LNPA-1100. The doping atomic percentages in LNPA-1100 are: 1.25% N, 1.28% P. In the Tafil curve of the oxygen reduction reaction zone, the slope of LNPA-1100 was 46.8 mVdecade -1 As shown in fig. 7; in the Tafil curve of the oxygen evolution reaction zone, the slope of LNPA-1100 was 168 mVdecade -1 As shown in fig. 8.
Example 5
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then 5mmol ethylenediamine is added with stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 10; adding 15mmol of acetaldehyde, heating to 60 ℃, then further heating to 110 ℃, refluxing for 6 hours, filtering, separating, and vacuum drying for 10 hours at 50 ℃ to obtain amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding 8 ml of hydroxyethylidene diphosphonic acid solution with the mass concentration of 10wt% and reacting for 2 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product at a high temperature of 900 ℃ for 4 hours in a nitrogen atmosphere, and finally obtaining various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Example 6
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then 0.5mmol ethylenediamine is added with stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 10; adding 10mmol of acetaldehyde, heating to 90 ℃, then further heating to 120 ℃, refluxing for 3 hours, filtering, separating, and vacuum drying for 11 hours at 45 ℃ to obtain amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding a methionine solution with the mass concentration of 70wt% into the mixture of 20 and ml, and reacting for 3 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product at 1100 ℃ in a nitrogen atmosphere for 1h to finally obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Example 7
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then 30mmol of ethylenediamine is added with stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 10; adding 20mmol of acetaldehyde, heating to 85 ℃, then further heating to 100 ℃, refluxing for 4 hours, filtering, separating, and vacuum drying for 8 hours at 60 ℃, thus obtaining amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding 1 ml mass percent of 50 weight percent paraphenyldiboronic acid solution, and reacting for 4 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product at 900 ℃ in a nitrogen atmosphere for 5 hours to finally obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Example 8
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then adding 20mmol of ethylenediamine under stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 9; adding 15mmol of acetaldehyde, heating to 70 ℃, then further heating to 100 ℃, refluxing for 4 hours, filtering, separating, and vacuum drying for 10 hours at 55 ℃, thus obtaining amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding a phytic acid solution with the mass concentration of 5 ml being 50wt% and a methionine solution with the mass concentration of 5 ml being 70wt% to react for 3 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product at 1000 ℃ in a nitrogen atmosphere for 3 hours to finally obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Example 9
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then adding 15mmol of ethylenediamine under stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 10; adding 10mmol of acetaldehyde, heating to 85 ℃, then further heating to 110 ℃, refluxing for 5 hours, filtering, separating, and vacuum drying for 12 hours at 40 ℃, thus obtaining amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding 5 ml of phytic acid solution with the mass concentration of 50wt% and 5 ml of terephthal-boric acid solution with the mass concentration of 50wt% to react for 3 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product at 1100 ℃ in a nitrogen atmosphere for 3 hours to finally obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Example 10
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then 10mmol ethylenediamine is added with stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 11; adding 10mmol of acetaldehyde, heating to 85 ℃, then further heating to 100 ℃, refluxing for 4 hours, filtering, separating, and vacuum drying for 12 hours at 45 ℃ to obtain amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding a solution of terephthalic acid with the mass concentration of 10 ml being 50wt% and a solution of methionine with the mass concentration of 10 ml being 70wt% to react for 3 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product for 4 hours at 800 ℃ under nitrogen atmosphere to finally obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
Example 11
The embodiment provides a preparation method for converting lignin into a plurality of different-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction, which comprises the following steps:
step S1, adding lignin 1g into 10 ml deionized water, and stirring by ultrasonic until the lignin is fully dispersed; then adding 20mmol of ethylenediamine under stirring; adding 0.2M sodium hydroxide aqueous solution, and adjusting the pH value to 10; adding 20mmol of acetaldehyde, heating to 80 ℃, then further heating to 100 ℃, refluxing for 4 hours, filtering, separating, and vacuum drying for 12 hours at 40 ℃, thus obtaining amino-lignin;
step S2, uniformly dispersing the 1g amino-lignin in 200 ml deionized water through ultrasonic treatment and stirring; then adding 3 ml mass concentration of 50wt% of terephthal acid solution, 3 ml mass concentration of 70wt% of methionine solution and 3 ml mass concentration of 50wt% of phytic acid solution, and reacting for 3 hours at room temperature; filtering and separating, washing for many times by deionized water, and removing redundant reactants; adjusting the pH value to 7, and obtaining a multi-atom doped amino-lignin product after freeze drying;
and S3, calcining the multi-atom doped amino-lignin product for 2 hours at 1200 ℃ in a nitrogen atmosphere to finally obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts.
FIG. 2 is an electron microscope scan of a variety of heteroatomic doped nano carbon-based composite nonmetallic materials LNPA-1000 obtained after calcination, the product is in a nano sphere shape, the specific surface area of the nano material is larger, and the electrocatalytic activity of the material is also greatly improved. FIG. 3 is an XPS diagram of various different atom doped nano carbon based composite nonmetallic materials obtained after calcination, three curves from top to bottom in FIG. 3 correspond to LNPA-900, LNPA-1000 and LNPA-1100 respectively, and doped different atoms exist in the obtained product as can be seen from FIG. 3.
FIG. 4 shows an IR spectrum of the PA, lignon-NH of FIG. 4 for different materials 2 The lignin, TEPA are phytic acid, amino-lignin, tetraethylenepentamine, respectively, and the LNP is lignin after doping nitrogen and phosphorus elements in step S2 of this example before high temperature calcination, and fig. 4 demonstrates that functional groups in phytic acid are successfully doped into lignin in the doping step before calcination.
FIG. 5 (a) is an X-ray diffraction diagram of carbon nitride and carbon phosphide in the carbon-based composite nonmetallic nanoparticle, three curves in FIG. 5 (a) are respectively LNPA-900, LNPA-1000 and LNPA-1100,cummulative curve from bottom to top, the curves are respectively overlapped with LNPA-900, XRD characteristic peaks (peak 1-6) in FIG. 5 (a) are respectively PC (002), tri-s-triazine-C3N 4 (100), graphitic carbon (200), g-C3N4 (20), PC (004)/g-C3N 4 (002) (020) and g-C3N4 (012)/(021), and FIG. 5 (a) proves that PC and g-C3N4 are simultaneously generated in the calcined product; FIGS. 5 (b) - (C) further illustrate the co-presence of PC and g-C3N4 in carbon-based materials.
FIG. 6 qualitatively demonstrates the successful doping of nitrogen and phosphorus elements in examples 2-4, which control the doping concentration of N, P by controlling the calcination temperature, together with FIGS. 7-9, illustrates the best performance of the calcined product at about 1000 ℃. In FIG. 7, from left to right, the first curve is LNPA-900, the second curve is LNPA-1100, and the third curve is LNPA-1000; in FIG. 8, from left to right, the first curve is LNPA-1100, the second curve is LNPA-900, and the third curve is LNPA-1000. The time-current diagram of the product prepared in the example 3 of fig. 9 under the conditions of 0.4V vs standard hydrogen evolution potential 0.1M potassium hydroxide and rotating speed of 800 rpm proves that the prepared material has better stability in the electrocatalytic field, wherein 93% of the curve corresponds to LNPA-1000, 81% of the curve corresponds to Pt/C, the attenuation degree of the LNPA-1000 prepared in the example is 7%, and the attenuation degree is better than that of the reference Pt/C, so that the nonmetallic catalytic material prepared in the example has better stability.
The foregoing description is only of the preferred embodiments of the present invention and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention are included in the protection scope of the present invention.
Claims (7)
1. The preparation method for converting lignin into various hetero-atom doped nano carbon-based composite nonmetallic catalysts through surface interface reaction is characterized by comprising the following steps of:
s1, preparing amino-lignin;
s2, dissolving amino-lignin in deionized water, performing ultrasonic treatment, adding at least one of a phosphorus-containing organic acid solution, a boron-containing organic acid solution and a sulfur-containing organic acid solution, reacting for 2-4 hours at room temperature, filtering, washing for many times, adjusting the pH value to be neutral, and performing freeze drying to obtain a polyatomic doped amino-lignin product;
s3, calcining the multi-atom doped amino-lignin product at high temperature in nitrogen or argon atmosphere to obtain various hetero-atom doped nano carbon-based composite nonmetallic catalysts;
the specific process of step S1 is as follows:
mixing the lignin after acid washing with amino-containing organic matters and aldehyde organic matters, adjusting the pH value to 9-11, heating, adding isopropanol, filtering, separating and vacuum drying to obtain amino-lignin;
the amino-containing organic matter comprises tetraethylenepentamine, ethylenediamine, m-phenylenediamine and 2, 3-diaminopyridine;
the mass ratio of lignin to the organic matters containing amino groups is (1:0.1) - (1:5);
the heating in the step S1 is divided into two steps, wherein the heating temperature in the first step is 60-90 ℃, the heating temperature in the second step is 100-120 ℃, and the reflux is carried out for 3-6 hours after the heating in the second step.
2. The method for preparing the nano carbon-based composite nonmetallic catalyst doped with different atoms, which is used for converting lignin into various different atoms through surface interface reaction according to claim 1, wherein the phosphorus-containing organic acid in the step S2 comprises hydroxyethylidene diphosphonic acid, aminotrimethylene phosphonic acid and phytic acid, the sulfur-containing organic acid comprises cystine, cysteine and methionine, and the boron-containing organic acid comprises terephthal-boric acid, trimethyl borate, triethyl borate and triisopropyl borate.
3. The method for preparing the carbon nano-based composite nonmetallic catalyst with different atoms doped by surface interface reaction for converting lignin into various different atoms according to claim 1, wherein the calcination temperature in the step S3 is 800-1200 ℃ and the calcination time is 1-5 hours.
4. The method for preparing the nano carbon-based composite nonmetallic catalyst with the surface interface reaction for converting lignin into various hetero atoms according to claim 1, wherein in the step S2, when 1g of amino-lignin is added, the total amount of the added phosphoric acid-containing organic solution, the added sulfuric acid-containing organic solution and the added boron-containing organic solution is 1-20 ml, and the mass concentration of the added phosphoric acid-containing organic solution, the added sulfuric acid-containing organic solution and the added boron-containing organic solution is 10-70 wt%.
5. The method for preparing the carbon nano-based composite nonmetallic catalyst for converting lignin into various hetero atoms through surface interface reaction according to claim 1, wherein the aldehyde organic matters comprise formaldehyde and glyoxal.
6. The method for preparing the carbon nano-based composite nonmetallic catalyst for converting lignin into various hetero atoms through surface interface reaction according to claim 1, wherein the drying temperature of vacuum drying is 40-60 ℃ and the drying time is 8-12h.
7. The method for preparing the nano carbon-based composite nonmetallic catalyst with the heteroatomic doping, which is used for converting lignin into various heteroatomic doping by surface interface reaction according to claim 1, wherein in the step S1, 1g of lignin is added, and 0.1-30 mmol of amino-containing organic matters and 10-20 mmol of aldehyde organic matters are correspondingly added.
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