CN108246330A - A kind of method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling - Google Patents
A kind of method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling Download PDFInfo
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- CN108246330A CN108246330A CN201810029041.1A CN201810029041A CN108246330A CN 108246330 A CN108246330 A CN 108246330A CN 201810029041 A CN201810029041 A CN 201810029041A CN 108246330 A CN108246330 A CN 108246330A
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- lignin
- metal
- catalyst
- monatomic
- monatomic catalyst
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 54
- 239000002184 metal Substances 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 229920005610 lignin Polymers 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 14
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 238000005245 sintering Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 31
- 229910017052 cobalt Inorganic materials 0.000 claims description 30
- 239000010941 cobalt Substances 0.000 claims description 30
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims 2
- GAEKPEKOJKCEMS-UHFFFAOYSA-N gamma-valerolactone Chemical compound CC1CCC(=O)O1 GAEKPEKOJKCEMS-UHFFFAOYSA-N 0.000 claims 2
- 229920001732 Lignosulfonate Polymers 0.000 claims 1
- 229920000877 Melamine resin Polymers 0.000 claims 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims 1
- 239000003513 alkali Substances 0.000 claims 1
- 239000004202 carbamide Substances 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 235000019441 ethanol Nutrition 0.000 claims 1
- 239000001307 helium Substances 0.000 claims 1
- 229910052734 helium Inorganic materials 0.000 claims 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims 1
- 239000012046 mixed solvent Substances 0.000 claims 1
- 238000012986 modification Methods 0.000 claims 1
- 230000004048 modification Effects 0.000 claims 1
- 239000003960 organic solvent Substances 0.000 claims 1
- 229910052704 radon Inorganic materials 0.000 claims 1
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 5
- 239000003446 ligand Substances 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 238000001556 precipitation Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 230000002950 deficient Effects 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- 235000013495 cobalt Nutrition 0.000 description 30
- 239000011943 nanocatalyst Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 8
- -1 graphite alkene Chemical class 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- QPJVMBTYPHYUOC-UHFFFAOYSA-N methyl benzoate Chemical compound COC(=O)C1=CC=CC=C1 QPJVMBTYPHYUOC-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000002105 nanoparticle Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 239000003643 water by type Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 235000019445 benzyl alcohol Nutrition 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229940095102 methyl benzoate Drugs 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 2
- 238000000833 X-ray absorption fine structure spectroscopy Methods 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000000231 atomic layer deposition Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960004217 benzyl alcohol Drugs 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000000731 high angular annular dark-field scanning transmission electron microscopy Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 238000006709 oxidative esterification reaction Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229910052573 porcelain Inorganic materials 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical group O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 208000020584 Polyploidy Diseases 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 150000003938 benzyl alcohols Chemical class 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002003 electron diffraction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 150000001455 metallic ions Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/391—Physical properties of the active metal ingredient
-
- 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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
A kind of method for being built into monatomic catalyst based on lignin/metal supermolecular assembling, belongs to catalysis material and prepares and lignin applied technical field.Key step includes：1) by certain density lignin and metal ion solution mixing, by adjusting pH, lignin/metal sublayer Supramolecular Assembling precipitation is formed；2) it centrifuges, it is dry, obtain catalyst precursor.3) presoma is mixed with nitrogen source, and under inert gas shielding, program high temperature sintering is to get the monatomic catalyst of metal.Compared with prior art; the present invention has cost of material low (lignin is ligand and carrier), (pH regulates and controls presoma and pickling-free stripping) simple for process, the metal dispersion uniformly distinguishing features such as (ligand complex and the regulation and control of increase defective bit), it is easy to accomplish the large-scale production of the monatomic catalyst of metal.
Description
Technical field
Patent of the present invention belongs to catalysis material and prepares and lignin applied technical field, and in particular to one kind based on wooden
The method that monatomic catalyst is constructed in element/metal supermolecular assembling.
Background technology
Supported, heterogeneous catalyst reduces catalyst cost, reduces ring for the recyclability and stability of raising catalyst
Border pollution is of great significance, and has extensively in the fields such as energy storage and conversion, organic synthesis, medicine preparation and environmental improvement
Using.Research shows that：The active constituent of load type metal catalyst is mainly metal, and active site then concentrates on particle surface
Atom.Therefore, it is the effective ways for improving metallic catalyst activity and selectivity to synthesize smaller size of particle.
In recent years, the monatomic catalyst of metal realizes the maximum utilization ratio of atom, shows high activity and high selection
Property, the catalytic efficiency of the monatomic catalyst of some non-precious metals has been over commercialization noble metal catalyst.Researcher recognizes
For monatomic catalyst is the bridge of framework multiphase and homogeneous catalysis.However, since single metal atom has very high surface
Free energy is easily gathered into cluster or nano particle in preparation process, it is more difficult to obtain monatomic.It can be seen that metal is monatomic
There are still lot of challenges for the preparation of catalyst, essentially consist in and how to be effectively anchored metallic atom, increase between metal and carrier
Interaction.
Up to now, many technologies of preparing in relation to the monatomic catalyst of metal are reported in succession, such as the precipitation method, dipping
Method, sol-gal process and atom seizure method etc., metal ligand and carrier material are related to metal oxide, graphene, carbon nanotube
Deng, these methods significant contribution is made that for improving the monatomic catalyst activity of metal and studying its mechanism of catalytic reaction.Specially
Sharp (CN107346826A, 2017) discloses a kind of redox elctro-catalyst preparation method of monatomic iron dispersion, the technique
It is dissolved, is retained with the iron atom of nitrogen coordination, so as to obtain using the unstable iron nano-particle that acid loads nitrogen-doped carbon
The metal iron catalyst of single atomic dispersion.This, which is that one kind is common, prepares the monatomic catalyst method of metal, and technique is simpler.But
It is that the technology can generate a large amount of acid waste liquid, pollutes environment, and there are the problems such as equipment corrosion.Document (Yan H.et
al.Single-Atom Pd1/Graphene Catalyst Achieved by Atomic Layer Deposition:
Remarkable Performance in Selective Hydrogenation of 1,3-
Butadiene.J.Am.Chem.Soc.2015,137(33):10484-10487) report using technique for atomic layer deposition in oxygen
Carried metal palladium on graphite alkene, prepares monatomic palladium catalyst, however, this method is low there are content of metal, and needs high
Your equipment can not mass produce.Document (Jones J.et al.Thermally stable single-atom
platinum-on-ceria catalysts via atom trapping.
Science.2016.353(6295):It 150-154) reports a kind of utilization atom seizure and prepares CeO 2 supporting
The monatomic catalyst of platinum should become volatility PtO it is a technical advantage that using Pt in the case where high temperature has Oxygen Condition2, by polyploid
Ceria captures.But this method universality is poor.To sum up, there are works for the existing method for preparing the monatomic catalyst of metal
The deficiencies of skill is complicated, cost of material is high, yield is small, universality is poor and environmental pollution is serious, up to now, still without a kind of method
It can realize that low-cost industrial produces the monatomic catalyst of metal.
Invention content
It is an object of the invention to develop a kind of side that monatomic catalyst is constructed based on lignin/metal supermolecular assembling
Method.Mainly include following steps：
(1) by certain density lignin and metal ion solution mixing, by adjusting pH, lignin/metal sublayer is formed
Supramolecular Assembling precipitates；
(2) it centrifuges, it is dry, obtain catalyst precursor.
(3) presoma is mixed with nitrogen source, and under inert gas shielding, program high temperature sintering is to get monatomic catalyst.
The present invention utilizes Coordinative Chemistry, is regulated and controled by pH, and metal ion is made to form Supramolecular Assembling complex with lignin,
Lignin causes metal ion to form single dispersion atom on spatial position as organic ligand.In order to increase metal target original
Spacing between son, by introducing metal zinc ion, when sintering temperature is higher than 800 DEG C, metallic zinc volatilization makes lignin carbon table
There are more defective bits in face.In high-temperature sintering process, lignin is gradually carbonized, and nitrogen source, which is gradually decomposed, generates ammonia doping to carbon
On, pyridine nitrogen, pyrroles's nitrogen are formed, is coordinated as anchored site and metal, enhances the interaction between carrier and metal, avoids
The reunion of metallic atom under high temperature finally obtains the monatomic catalyst of nitrogen-doped carbon carried metal.
Compared with prior art, the technology of the present invention advantage is：(1) using the lignin of biomass source as organic ligand
And carbon source, low in raw material price is renewable, meets sustainable development and green manufacturing theory；(2) compared to smaller ligand and
Speech, lignin is natural aromatic class macromolecule polyalcohol, and metallic ion coordination, can increase space between metallic atom away from
From；(3) lignin/metal supermolecular assembling can be operated, condition as catalyst precursor in room temperature and aqueous solution
Mildly, low energy consumption, pollution-free；(4) the monatomic catalyst of metal can be obtained after high temperature sintering, does not need to pickling stripping washing step
Suddenly, it is discharged without " three wastes "；(5) it is simple for process, universality is wide, at low cost, be easy to industrialization amplification production.
Description of the drawings
(by taking metallic cobalt as an example)：
Fig. 1 is the monatomic XRD spectra with nanocatalyst of metallic cobalt.
Fig. 2 is that the HAADF-STEM of the monatomic catalyst of metallic cobalt schemes.
Fig. 3 is that the XAFS of the monatomic catalyst of metallic cobalt schemes.
Fig. 4 is that the TEM of metallic cobalt nanocatalyst schemes：A) catalyst entirety TEM schemes；B) part of single cobalt nano-particle
Amplify high-resolution TEM figures；C) electron diffraction diagram.
Fig. 5 is that metallic cobalt is monatomic and nanocatalyst, catalytic phenylmethanol prepare the activity rating of methyl benzoate.
Fig. 6 is flow diagram of the present invention.
Specific embodiment：
By the following example and with reference to attached drawing, the invention will be further described, but invention content is not limited solely to reality
Apply example.
Embodiment 1：The synthesis of the monatomic catalyst precursor of metal
1) 8g lignin is dissolved in 1L deionized waters, wiring solution-forming A.Zinc nitrate hexahydrate (11.90g, 40mmol Zn2+) and
Cabaltous nitrate hexahydrate (2.33g, 8mmol Co2+) it is dissolved in 0.5L deionized waters, wiring solution-forming B.
2) solution B is added in solution A, with the quick mixing of mechanical agitation, pH is nature (pH~6.1), mixture after
Continuous stirring 1h, then stands overnight at room temperature.
3) supernatant is outwelled, 5,000 × g centrifugation 10min, 80 DEG C of precipitation is dried overnight, and obtains the monatomic catalysis of metallic cobalt
Agent presoma, is named as Co1Zn5-L。
4) similarly, change metallic cobalt into other metal ions, such as iron, nickel, copper, manganese, zirconium, molybdenum, obtain lignin/
Metal supermolecular assembles, and is named as M1Zn5(M represents metal ion, such as Fe to-L3+,Ni2+,Cu2+,Mn2+, Zr2+,Mo2+；L represents wood
Quality).
In order to prove effect of the metallic zinc in catalyst precursor synthesis, we have synthesized metal nano complex catalyst precursor
Body, example, step are as follows as a comparison：
1) 8g lignin is dissolved in 1L deionized waters, wiring solution-forming A.Cabaltous nitrate hexahydrate (5.82g, 20mmol Co2+) be dissolved in
0.5L deionized waters, wiring solution-forming B.
2) solution B is added in solution A, with the quick mixing of mechanical agitation, solution adjusts pH with 10wt.% ammonium hydroxide and arrives
7.4, mixture continues to stir 1h, then stands overnight at room temperature.
3) supernatant is outwelled, after 5,000 × g centrifugations 10min, 80 DEG C of precipitation is dried overnight, and obtains metallic cobalt nano-catalytic
Agent presoma, is named as Co2.5-L.The unified complete entitled M of other metal nano catalyst precursors2.5- L (M represents metal ion,
Such as Fe3+,Ni2+,Cu2+,Mn2+, Zr2+,Mo2+；L represents lignin).
Embodiment 2：The synthesis of the monatomic catalyst of metal
1) 0.1g lignin/metallic cobalt catalyst precursor Co is taken1Zn5- L and 1g dicyandiamides, are fully ground mixing.
2) powder of milled is put into porcelain boat, be placed in tube furnace, argon gas flow velocity is 75mL/min, and temperature program is：From
Room temperature is warming up to 550 DEG C with 5 DEG C/min, keeps 1h, then be warming up to 900 DEG C with 5 DEG C/min, room is naturally cooled to after keeping the temperature 3h
Temperature obtains the monatomic catalyst of cobalt of nitrogen-doped carbon load.
3) similarly, change lignin/metallic cobalt catalyst precursor into other metal ion presomas, as iron, nickel,
The lignin of copper, manganese etc./metal supermolecular assembling M1Zn5(M represents metal ion, such as Fe to-L3+,Ni2+,Cu2+,Mn2+, Zr2+,
Mo2+；L represents lignin), with 1g dicyandiamides, it is fully ground mixing.Metal precursor is 1 with dicyandiamide mass ratio:10, program
900 DEG C are warming up to, high temperature sintering obtains the monatomic catalyst of metal of nitrogen-doped carbon load.
4) other conditions are constant, using methylimidazole as nitrogen source；Or keep other conditions constant, metal precursor with it is double
Cyanamide mass ratio is 1:50；Or other conditions are constant, temperature programming to 1100 DEG C, high temperature sintering can obtain nitrogen-doped carbon
The monatomic catalyst of metal of load.
Example as a comparison, by metal precursor M1Zn5- L changes M into2.5(M represents metal ion, such as Fe to-L3+,Ni2+,Cu2 +,Mn2+, Zr2+,Mo2+；L represents lignin), mixing is fully ground with nitrogen source, is put into porcelain boat, is placed in tube furnace, argon gas flow velocity
For 75mL/min, temperature program is：550 DEG C are warming up to from room temperature with 5 DEG C/min, keeps 1h, then 900 are warming up to 5 DEG C/min
DEG C, room temperature is naturally cooled to after keeping the temperature 3h, obtains metal nano catalyst.
Embodiment 3：The activity rating of the monatomic catalyst of metal
1) 10mL methanol, 1mmol benzyl alcohols and the monatomic catalysis of 2.5mol% metallic cobalts are added in 100mL round-bottomed flasks
Agent, 0.25mmol methyl phenyl ethers anisoles are as internal standard.
2) first with it is pure oxygen replaced fall round-bottomed flask in air, in 1bar O2(oxygen ball) is reacted under the conditions of 60 DEG C, fixed
When sample, with HPLC analyze reaction product.Analysis condition is：Chromatographic column C18,30 DEG C of column temperature, 30% acetonitrile of mobile phase and 70%
Water (trifluoroacetic acid containing 0.05v%), flow velocity 1mL/min, UV detector 254nm.
3) catalyst is changed into the monatomic catalyst of other metals (such as iron, nickel, copper, manganese, zirconium, molybdenum), catalytic phenylmethanol
Methyl benzoate is prepared with methanol oxidative esterification, reaction system and product testing condition are constant.
4) example as a comparison, the monatomic catalyst of metal change metal nano catalyst into, addition 5.5mol%,
The catalytic effect of metal nano catalyst is evaluated, by calculating transformation frequency (TOF), compares the monatomic catalyst of metal and metal
The catalytic effect of nanocatalyst.
The monatomic catalyst XRD spectra of metallic cobalt does not observe metallic cobalt or its oxide it can be seen from attached drawing 1
Diffraction maximum, it is high degree of dispersion on carrier to illustrate cobalt.However, the XRD spectra of metallic cobalt nanocatalyst occurs significantly
Metallic cobalt diffraction maximum.In order to further determine the dispersibility of cobalt on the monatomic catalyst of metallic cobalt, attached drawing 2 passes through HAADF-STEM
It observes that cobalt atom is single to be dispersed on carrier.Attached drawing 3 is analyzed by XAFS further determined that metallic cobalt is monatomic and urges
The fine structure of agent, catalytic activity region are Co-Nx-C.Attached drawing 4 by TEM find metallic cobalt nanocatalyst on cobalt be by
The nano particle of graphite-phase carbon package, high-resolution TEM and electronic diffraction determine that cobalt is existed in the form of metallic cobalt.
By taking the oxidative esterification methyl benzoate of benzyl alcohol as an example, attached drawing 5 compares that metallic cobalt is monatomic and cobalt nano-catalytic
The catalytic efficiency of agent.As can be seen that the catalytic rate of the monatomic catalyst of metallic cobalt is significantly better than nanoparticle catalyst, conversion
Frequency (TOF) is 18.3 times (be calculated during methyl benzoate yield 50%) of cobalt nanocatalyst.
Claims (6)
- A kind of 1. method that monatomic catalyst is constructed based on lignin/metal supermolecular assembling, which is characterized in that including following Step：1) by certain density lignin and metal ion solution mixing, by regulating and controlling pH, lignin/metal sublayer supermolecule is formed Assembling；Metal ion molal weight is 0.5-50mmol metals/g lignin with lignin weight ratio；PH modification scopes are 2-10；2) it centrifuges, it is dry, obtain catalyst precursor；3) catalyst precursor is mixed with nitrogen source, and the mass ratio of nitrogen source and catalyst precursor is 0.5-50；It is protected in inert gas Under shield, high temperature sintering, 900-1100 DEG C of high temperature sintering temperature, program temperature is：5 DEG C/min is warming up to 550 DEG C, keeps the temperature 1h, so It is warming up to 900-1100 DEG C again afterwards, after keeping the temperature 4h, naturally rings to room temperature；Sintered catalyst is ground to get monatomic Catalyst.
- 2. the method as described in claim 1, which is characterized in that lignin includes alkali lignin, organic solvent lignin, enzymolysis Lignin, lignosulfonates.
- 3. the method as described in claim 1, which is characterized in that metal ion includes manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum.
- 4. the method as described in claim 1, which is characterized in that the solvent of dissolved lignin and metal ion solution include water, Dimethylformamide, gamma-valerolactone, tetrahydrofuran, dimethyl sulfoxide (DMSO), ethyl alcohol, methanol one of which or mixed solvent.
- 5. the method as described in claim 1, which is characterized in that nitrogen source includes ammonia, urea, dicyandiamide, melamine, nitridation Carbon, cyanamide, methylimidazole；The weight mass ratio of nitrogen source and catalyst precursor is 0.5-50.
- 6. the method as described in claim 1, which is characterized in that inert gas includes nitrogen, argon gas, helium, radon gas wherein one Kind.
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