CN114107405B - Method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst by lignocellulose biomass - Google Patents
Method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst by lignocellulose biomass Download PDFInfo
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 52
- 239000002028 Biomass Substances 0.000 title claims abstract description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 26
- 239000001301 oxygen Substances 0.000 title claims abstract description 26
- 239000002253 acid Substances 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 title claims abstract description 24
- 230000009467 reduction Effects 0.000 title claims abstract description 21
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 19
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 title claims abstract description 8
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 47
- 238000000197 pyrolysis Methods 0.000 claims abstract description 25
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 21
- 125000000524 functional group Chemical group 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000002054 inoculum Substances 0.000 claims abstract description 9
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000007788 liquid Substances 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 230000033228 biological regulation Effects 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
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- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 235000005985 organic acids Nutrition 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 230000007935 neutral effect Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000012163 sequencing technique Methods 0.000 claims description 5
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- 239000010871 livestock manure Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 240000006248 Broussonetia kazinoki Species 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 16
- 230000000813 microbial effect Effects 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 241001052560 Thallis Species 0.000 abstract description 4
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 6
- 239000003610 charcoal Substances 0.000 abstract 1
- 244000005700 microbiome Species 0.000 abstract 1
- 238000004064 recycling Methods 0.000 abstract 1
- 239000007790 solid phase Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 19
- 238000000855 fermentation Methods 0.000 description 16
- 230000004151 fermentation Effects 0.000 description 14
- 241000933832 Broussonetia Species 0.000 description 11
- 239000011148 porous material Substances 0.000 description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 239000000446 fuel Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 241000705930 Broussonetia papyrifera Species 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
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- 241000209046 Pennisetum Species 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229920005610 lignin Polymers 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 240000000731 Fagus sylvatica Species 0.000 description 2
- 235000010099 Fagus sylvatica Nutrition 0.000 description 2
- 229920002488 Hemicellulose Polymers 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000002029 lignocellulosic biomass Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000004281 Eucalyptus maculata Species 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- 240000006394 Sorghum bicolor Species 0.000 description 1
- 235000011684 Sorghum saccharatum Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
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- 238000011161 development Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000747 poly(lactic acid) Polymers 0.000 description 1
- 239000004626 polylactic acid Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2203/00—Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
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Abstract
The invention discloses a method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst by lignocellulose biomass. In particular to two processes of lignocellulose biomass acid production and charcoal production. Firstly, raw materials are subjected to a hydrothermal pretreatment mode, and then the pretreated raw materials and an inoculum are mixed, and acid production is carried out after the pH value of an acid production system is directionally regulated and controlled to 10-11. The solid-phase product in the acid production process is used for directional carbon production, the internal structure of biomass is opened due to the action of microorganisms, and simultaneously nitrogen-rich raw material microbial thalli are introduced, nitrogen is introduced into a carbon skeleton through high-temperature pyrolysis under inert atmosphere, so that rich nitrogen-containing functional groups are formed, the nitrogen-rich pyrolysis and conversion of lignocellulose biomass are realized, and finally the functional high-nitrogen-content porous carbon material with rich nitrogen-containing functional groups is formed, and has wide application prospects in the field of electrocatalysis, so that the high-value conversion and recycling utilization of lignocellulose biomass are realized.
Description
Technical Field
The invention belongs to the technical field of biomass utilization, and particularly relates to a method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst by lignocellulose biomass.
Background
Lignocellulosic biomass is the most abundant biomass resource on earth, and comprises wood (such as eucalyptus, beech, poplar and the like) and agricultural and forestry wastes (such as corn stalks, wheat stalks, sorghum stalks and the like), and has the characteristics of wide sources, universality, accessibility and the like. The lignocellulose biomass mainly comprises cellulose, hemicellulose, lignin and the like, and the lignocellulose biomass and the lignin are strongly meshed with each other through covalent bonds or non-covalent bonds, so that the plant has a stable three-dimensional pore structure. The unique pore structure provides convenience for constructing the carbon material with the complex hierarchical pore structure, but simultaneously, the strong crosslinking effect makes the morphology and structure of the product difficult to accurately regulate and control.
Doping (N, P, S, B, F and the like) of hetero atoms is an important strategy for improving the oxygen reduction performance of the carbon material, and particularly the introduction of the nitrogen-containing functional group plays a remarkable role in improving the electrochemical quality of the carbon material. The nitrogen atoms are similar in size to the carbon atoms and thus can easily replace the carbon atoms in the carbon nanomaterial. On the other hand, the N-doped atoms have higher electron affinity than the C atoms, which makes it easy for the N-doped atoms to change the atomic structure and electron arrangement in the carbon material, thereby leading to delocalization of charges in the carbon nanomaterial, variation in spin density, and increase in state density closer to the fermi level. These optimizations further give the carbon material n-type conductivity, increasing the metal properties, increasing the electron transfer rate, and providing more active sites for the reactants. The rich incorporation of nitrogen atoms allows the carbon-based material to exhibit different properties.
The existing patents on biochar electrode material preparation focus more on efficient conversion of nitrogen-rich biomass, such as (CN 104241662 a), mainly on pyrolysis process regulation of nitrogen-rich biomass. At present, no report is available on the preparation of the high-nitrogen-content porous carbon material through biological process regulation. Therefore, the development of the simple, low-cost and high-efficiency biomass-based nitrogen-doped hierarchical porous carbon material has important significance.
Disclosure of Invention
The first object of the invention is to provide a method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst from lignocellulose biomass.
The invention realizes nitrogen-rich pyrolysis and structure regulation of general lignocellulose biomass through biological process regulation and control. By surface modification and structure adjustment, heterogeneous doping and defect sites are formed in the porous carbon material, nano-scale pores, holes and channels are adjusted, the activity, selectivity and stability of the catalyst can be obviously improved, and the specific energy density of the battery is improved.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst from lignocellulosic biomass, comprising the steps of:
s1: pretreating lignocellulose biomass in a hydrothermal reaction kettle;
s2: transferring the pretreated material in the step S1 into an acid-producing reactor, adding an inoculum, adjusting the pH value, performing solid-liquid separation after running for a period of time, and collecting a liquid part rich in volatile organic acids;
S3: drying the solid part collected in the step S2, and then carrying out nitrogen-rich pyrolysis reaction in an inert atmosphere to obtain nitrogen-doped biochar;
S4: and (3) pickling the biochar obtained in the step (S3), washing with excessive deionized water until filtrate is neutral, and drying to obtain the functional high-nitrogen-content porous carbon material with rich nitrogen-content functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
Further, the pretreatment conditions in the step S1 are as follows: the solvent is water, the temperature is 160-200 ℃, the time is 2-6 h, and the solid-liquid ratio is 1:15-20.
Furthermore, the acid-producing reactor in the step S2 adopts a sequencing batch feeding mode, and the material retention time is 4-6 d; the pH value of the acid-producing reactor is regulated to 10-11, the operating temperature is 35-55 ℃, and the operating time is 4-10 d.
Further, the solid-liquid separation in the step S2 is performed by using a high-speed centrifuge.
Further, the temperature of the nitrogen-rich pyrolysis reaction in the step S3 is 600-1200 ℃, and the heating rate is 1-20 ℃/min.
Further, the regulation and control mode of the nitrogen-rich pyrolysis reaction process in the step S3 comprises activation regulation and control, and the regulation and control activator is at least one selected from KOH, znCl 2、K2CO3、HPO4, basic carbonate and ionic liquid.
Further, the lignocellulose biomass is at least one selected from straw, pennisetum, paper mulberry and beech.
The principle of the inventive concept is: firstly, hemicellulose and partial cellulose in lignocellulose biomass components are directionally degraded in an anaerobic fermentation process, so that loose structure is realized, the conversion rate of fibers of lignocellulose biomass raw materials in an anaerobic process is not high, about 20% -60% of fibers cannot be utilized, and unconverted cellulose and lignin have loose structures and smooth pore channels, so that the full infiltration of an activating agent is facilitated, and the pore channel structure abundance of a carbon product is improved. In addition, the loose pore canal provides a convenient condition for the uniform attachment of microbial thalli, so that the microbial thalli of the nitrogen-rich raw material can be uniformly attached to the raw material in the fermentation process, and a large number of residual microbial thalli can be used as the nitrogen-rich raw material to supplement nitrogen sources for biomass bodies, so that nitrogen enrichment is realized, and a necessary condition is provided for the pyrolysis conversion of the nitrogen-rich raw material; and in the nitrogen-rich pyrolysis process, part of carbon atoms generate gaseous and liquid products, and simultaneously, the nitrogen atoms are doped in the carbon atom combination process to form rich active nitrogen-containing functional groups (such as pyridine-N, pyrrole-N, graphite-N and the like), and finally, the functional high-nitrogen-content porous carbon material with rich active nitrogen-containing functional groups is formed, and has wide application prospects in the field of electrocatalysis, so that the high-added-value utilization of biomass is realized.
The second aim of the invention is to provide the high-nitrogen-content porous carbon material prepared by the method for co-producing the acid and the nitrogen-rich carbon-based oxygen reduction catalyst by using the lignocellulose biomass.
In the high-nitrogen-content porous carbon material, the existence form of nitrogen comprises pyridine-N, pyrrole-N or graphite-N.
The functional high-nitrogen-content porous carbon material obtained by the invention has developed pore structure and rich active nitrogen-content functional groups, and has wide application prospect, such as being used as an oxygen reduction catalyst, an electrode material and the like.
It is therefore a third object of the present invention to provide the use of the above-mentioned high nitrogen-containing porous carbon material as an oxygen reduction catalyst or electrode material.
The invention has the technical effects that:
1. In the method, the lignocellulose biomass is utilized to prepare the high-nitrogen porous carbon material, so that a high-value utilization method for biomass wastes can be provided.
2. In the method, the lignocellulose biomass is utilized to prepare the high-nitrogen porous carbon material, structural depolymerization and nitrogen enrichment are realized through anaerobic fermentation, and further nitrogen-rich pyrolysis is carried out, so that the porous carbon material with a hierarchical structure rich in nitrogen-containing functional groups (such as pyridine-N, pyrrole-N and graphite-N) is obtained.
3. According to the method, depolymerization and nitrogen enrichment of the lignocellulose biomass structure can be realized by adjusting the anaerobic fermentation process, the operation is simple, the control is easy, the cost is low, the high-nitrogen-content porous carbon material can be obtained through one-step nitrogen-rich pyrolysis, the specific surface area of the high-nitrogen-content porous carbon material reaches 1057.9m 2/g, and the nitrogen content reaches 8.32%; and the liquid oil and pyrolysis gas byproducts generated by nitrogen-rich pyrolysis can be further developed and utilized, such as liquid oil separation and purification to prepare high added value compounds and the like.
4. The functional high-nitrogen-content porous carbon material obtained by the method has developed pore structure and rich active nitrogen-content functional groups, and the nitrogen-content functional groups have good dispersibility and wide application prospects in the field of electrocatalysis.
5. The volatile organic acid prepared by the method can be used for chemical raw materials, and the obtained high-nitrogen-content porous carbon material can be applied to electrocatalytic oxygen reduction reaction. For example, lactic acid can be used for producing polylactic acid, and the high-nitrogen-content porous carbon material can be used for preparing materials of air cathode fuel cells such as microbial fuel cells, oxyhydrogen fuel cells and the like.
Drawings
FIG. 1 is an SEM image of the paper mulberry of example 1 before and after fermentation. The paper mulberry biogas residue in the figure is the paper mulberry after fermentation.
FIG. 2 is a N1s XPS spectrum of the high nitrogen-containing porous carbon material prepared in example 1 of the present invention. In the figure PYRIDINE N is pyridine N, pyrrolic N is pyrrole N, and GRAPHITIC N is graphite-N.
FIG. 3 is a graph showing the electrocatalytic oxygen reduction reaction of the paper mulberry of example 1 of the present invention without fermentation, the porous carbon material (g@C) obtained by direct pyrolysis, and the porous carbon material (gz@C) obtained by pyrolysis after fermentation of paper mulberry.
Detailed Description
In order that the above-recited objects of the present invention may be understood in detail, a more particular description of the invention is given below with reference to specific examples, although the scope of the invention is not limited to the following examples.
Example 1
A method for co-producing acid and high nitrogen-containing porous carbon material by using Broussonetia papyrifera comprises the following steps:
s1: crushing Broussonetia papyrifera, mixing with water according to a solid-to-liquid ratio of 1:20, and pretreating in a hydrothermal reaction kettle at 200 ℃ for 6 hours.
S2: transferring the pretreated material in the step S1 into an acid-producing reactor in a sequencing batch feeding mode, wherein the material residence time is 5d, adding livestock manure inoculums (VS Substrate(s) ：VS Inoculant =3:1), adjusting the pH value to 11, operating at 55 ℃ for 10d, and then adopting a high-speed centrifuge to separate solid from liquid, wherein the collected liquid part is rich in volatile organic acids, and the content of the organic acids can reach 10g/L.
S3: and (3) drying the solid part collected in the step (S2) to constant weight in an oven at 105 ℃ to obtain the raw material to be pyrolyzed.
S4: fully mixing the raw material to be pyrolyzed obtained in the step S3 with K 2CO3 according to the mass ratio of 1:1, adding 10mL of deionized water, magnetically stirring for 8 hours under the constant temperature condition, and placing the fully mixed suspension into a vacuum drying oven to be dried at 60 ℃ for later use.
S5: and (3) placing the dried solid in the S4 in a vacuum tube furnace, performing pyrolysis reaction at 900 ℃ in a nitrogen atmosphere, and annealing for 2 hours at a heating rate of 5 ℃/min to obtain the nitrogen-doped biochar.
S6: and (3) pickling the nitrogen-doped biochar obtained in the step (S5), wherein the concentration of a hydrochloric acid solution is 1mol/L, then washing with excessive deionized water until filtrate is neutral, and performing suction filtration and drying to obtain the functional high-nitrogen-content porous carbon material with rich nitrogen-containing functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
After the characterization of the obtained high-nitrogen-content porous carbon material, the result shows that the obtained material has a developed pore structure, the surface area reaches 1057.9m 2/g, the nitrogen content reaches 8.32%, and the material has rich active nitrogen-containing functional groups (pyridine-N, pyrrole-N and graphite-N).
The nitrogen content of paper mulberry before and after fermentation was measured, and the results are shown in Table 1. As shown in Table 1, nitrogen element is obviously improved after the fermentation of the paper mulberry, and is improved by 26.88% compared with the nitrogen element before the fermentation.
TABLE 1
FIG. 1 is an SEM image of the paper mulberry of example 1 before and after fermentation. As can be seen from the SEM image, after the paper mulberry is subjected to anaerobic fermentation, the structure is obviously changed, the original compact structure is damaged, and the surface is roughened, so that the adhesion of nitrogen-rich raw material microbial cells is more facilitated.
FIG. 2 is a N1s XPS spectrum of the high nitrogen-containing porous carbon material prepared in example 1 of the present invention. Experimental results show that the high-nitrogen-content porous carbon material has a developed pore structure, the surface area reaches 1057.9m 2/g, and the high-nitrogen-content porous carbon material has rich active nitrogen-containing functional groups (pyridine-N, pyrrole-N and graphite-N), and the nitrogen content reaches 8.32%.
FIG. 3 shows the oxygen reduction performance of the porous carbon material g@C (without fermentation treatment) obtained by direct pyrolysis of Broussonetia papyrifera, and the porous carbon material gz@C obtained by pyrolysis after fermentation of Broussonetia papyrifera. As can be seen from fig. 3, the initial potential of the catalytic oxygen reduction reaction of the porous carbon material prepared by the paper mulberry pyrolysis after fermentation treatment is obviously shifted forward, which indicates that the electrocatalytic oxygen reduction performance of the electrode carbon material prepared by pyrolysis is obviously improved.
The above results indicate that: the high-nitrogen-content porous carbon material prepared by the method can be applied to electrocatalytic oxygen reduction reaction. For example, it is used in air cathode fuel cells such as microbial fuel cells and oxyhydrogen fuel cells to catalyze oxygen reduction reaction.
Example 2
A method for co-producing acid and high nitrogen-containing porous carbon material by using hybrid pennisetum comprises the following steps:
s1: crushing the hybrid pennisetum, mixing with water according to the solid-to-liquid ratio of 1:15, and pretreating for 4 hours at 180 ℃ in a hydrothermal reaction kettle.
S2: transferring the pretreated material in the step S1 into an acid-producing reactor in a sequencing batch feeding mode, wherein the material residence time is 5d, adding livestock manure inoculums (VS Substrate(s) ：VS Inoculant =3:1), adjusting the pH to 10, operating for 4d at 35 ℃, and then separating by a high-speed centrifuge to perform solid-liquid separation, wherein the collected liquid part is rich in volatile organic acids, and the content of the organic acids can reach 5g/L.
S3: and (3) drying the solid part collected in the step (S2) to constant weight in an oven at 105 ℃ to obtain the raw material to be pyrolyzed.
S4: fully mixing the raw material to be pyrolyzed obtained in the step S3 with ZnCl 2 according to the mass ratio of 1:1, adding 10mL of deionized water, magnetically stirring for 8 hours under the constant temperature condition, and placing the fully mixed suspension into a vacuum drying oven to be dried at the temperature of 60 ℃ for later use.
S5: and (3) placing the dried solid in the S4 in a vacuum tube furnace, performing pyrolysis reaction at 1200 ℃ in a nitrogen atmosphere, and annealing for 2 hours at a heating rate of 20 ℃/min to obtain the nitrogen-doped biochar.
S6: and (3) pickling the nitrogen-doped biochar obtained in the step (S5), wherein the concentration of a hydrochloric acid solution is 1mol/L, then washing with excessive deionized water until filtrate is neutral, and performing suction filtration and drying to obtain the functional high-nitrogen-content porous carbon material with rich nitrogen-containing functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
Through detection, the surface area of the high-nitrogen-content porous carbon material prepared in the embodiment 2 of the invention reaches 1032.5m 2/g, and the nitrogen content reaches 5.23%.
Example 3
A method for co-producing acid and high nitrogen-containing porous carbon material by using crop straws comprises the following steps:
s1: crushing straw, mixing the crushed straw with water according to the solid-to-liquid ratio of 1:20, and carrying out pretreatment for 6h at 200 ℃ in a hydrothermal reaction kettle.
S2: transferring the pretreated material in the step S1 into an acid-producing reactor in a sequencing batch feeding mode, wherein the material residence time is 5d, adding livestock manure inoculums (VS Substrate(s) ：VS Inoculant =3:1), adjusting the pH to 10, operating at 35 ℃ for 6d, and then adopting a high-speed centrifuge to separate solid from liquid, wherein the collected liquid part is rich in volatile organic acids, and the content of the organic acids can reach 6g/L.
S3: and (3) drying the solid part collected in the step (S2) to constant weight in an oven at 105 ℃ to obtain the raw material to be pyrolyzed.
S4: fully mixing the raw material to be pyrolyzed obtained in the step S3 with K 2CO3 according to the mass ratio of 1:1, adding 10mL of deionized water, magnetically stirring for 8 hours under the constant temperature condition, and placing the fully mixed suspension into a vacuum drying oven to be dried at 60 ℃ for later use.
S5: and (3) placing the dried solid in the S4 in a vacuum tube furnace, performing pyrolysis reaction at 600 ℃ in a nitrogen atmosphere, and annealing for 2 hours at a heating rate of 1 ℃/min to obtain the nitrogen-doped biochar.
S6: and (3) pickling the nitrogen-doped biochar obtained in the step (S5), wherein the concentration of a hydrochloric acid solution is 1mol/L, then washing with excessive deionized water until filtrate is neutral, and performing suction filtration and drying to obtain the functional high-nitrogen-content porous carbon material with rich nitrogen-containing functional groups, namely the nitrogen-rich carbon-based oxygen reduction catalyst.
Through detection, the surface area of the high-nitrogen-content porous carbon material prepared in the embodiment 3 of the invention reaches 1135.2m 2/g, and the nitrogen content reaches 3.98%.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that the above-mentioned preferred embodiment should not be construed as limiting the invention, and the scope of the invention should be defined by the appended claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and such modifications and adaptations are intended to be comprehended within the scope of the invention.
Claims (3)
1. A method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst from lignocellulose biomass, which is characterized by comprising the following steps:
s1: crushing paper mulberry, and then pretreating in a hydrothermal reaction kettle under the following conditions: the solvent is water, the temperature is 200 ℃, the time is 6 hours, and the solid-liquid ratio is 1:20;
S2: transferring the pretreated material in the step S1 into an acid-producing reactor in a sequencing batch feeding mode, wherein the material residence time is 5d, adding livestock manure inoculums, adjusting the operating pH value of the acid-producing reactor to 11, operating the temperature to 55 ℃ and the operating time to 10d, and then adopting a high-speed centrifuge to carry out solid-liquid separation, wherein the collected liquid part is rich in volatile organic acids;
s3: drying the solid part collected in the step S2, and then carrying out nitrogen-rich pyrolysis reaction under an inert atmosphere, wherein the temperature of the nitrogen-rich pyrolysis reaction is 900 ℃, the heating rate is 5 ℃/min, the regulation and control mode of the nitrogen-rich pyrolysis reaction process comprises activation regulation and control, and the regulation and control activator of the activation regulation and control is K 2CO3 to obtain the nitrogen-doped biochar;
S4: washing the biochar obtained in the step S3 with excessive deionized water until the filtrate is neutral, and drying to obtain a functional high-nitrogen-content porous carbon material with rich nitrogen-content functional groups, namely a nitrogen-rich carbon-based oxygen reduction catalyst; the nitrogen-rich carbon-based oxygen reduction catalyst comprises the following nitrogen forms including pyridine-N, pyrrole-N and graphite-N, wherein the nitrogen content is 8.32%, and the percentage ratio of the three nitrogen forms is as follows: pyridine-N: pyrrole-N: graphite-n=53.8: 40.5:5.7.
2. The high nitrogen-containing porous carbon material prepared by the method for co-producing acid and nitrogen-rich carbon-based oxygen reduction catalyst by using lignocellulose biomass according to claim 1.
3. Use of the high nitrogen-containing porous carbon material according to claim 2 as an oxygen reduction catalyst or electrode material.
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| CN110474057A (en) * | 2019-08-30 | 2019-11-19 | 太原理工大学 | A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon |
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| CN110474057A (en) * | 2019-08-30 | 2019-11-19 | 太原理工大学 | A kind of preparation method and application of the oxygen reduction electro-catalyst based on lignocellulose-like biomass carbon |
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