CN111715256B - Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles - Google Patents

Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles Download PDF

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CN111715256B
CN111715256B CN202010524199.3A CN202010524199A CN111715256B CN 111715256 B CN111715256 B CN 111715256B CN 202010524199 A CN202010524199 A CN 202010524199A CN 111715256 B CN111715256 B CN 111715256B
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silk fibroin
doped
porous carbon
carbon aerogel
based nitrogen
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CN111715256A (en
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吕晓萌
肖新新
龚善和
王文搏
刘军
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Jiangsu University
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    • 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
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    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • B01J35/394—Metal dispersion value, e.g. percentage or fraction
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Abstract

The invention belongs to the technical field of nano material preparation, and particularly relates to a preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles. Extracting silk fibroin from silkworm cocoon, adding silk fibroin solution into aqueous solution of copper salt and zinc salt, and adding CO 2 And uniformly dispersing metal salt in the silk fibroin solution in a bubbling mode to form hydrogel, and performing freeze drying and high-temperature carbonization to obtain the silk fibroin-derived nitrogen-doped porous carbon aerogel dispersed copper nanoparticles. The method has the advantages of green and environment-friendly raw materials, simple process, low generation cost, small size of copper nanoparticles, realization of industrial production, high yield and the like. The material prepared by the method is used for electrochemical reduction of CO 2 And in addition, the catalyst has high catalytic activity and stability, and the Faraday efficiency of the product CO is high.

Description

Preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles
Technical Field
The invention belongs to the technical field of nano-material preparation, and relates to a preparation method for preparing a nitrogen-doped carbon aerogel dispersed copper nanoparticle composite material by taking silk fibroin as a nitrogen-doped/porous carbon aerogel precursor through sol-gel and pyrolysis.
Technical Field
At present, fossil fuels are the main energy source for maintaining national economy, and the massive combustion of fossil fuels results in carbon dioxide (CO) in the environment 2 ) The concentration is increased continuouslyCausing serious environmental problems and threatening the sustainable development of human beings. Electrocatalytic CO 2 Reduction reaction (eCO) 2 RR) has mild conditions, is simple and easy to operate, and is widely researched. However, this process is kinetically slow due to the multiple electron transfer steps and high reaction energy barriers involved. Thus, there is a need for effective electrocatalysts to lower the reaction energy barrier and to promote the reaction kinetics to achieve commercially significant rates. Electrochemical reduction of CO 2 Among the metal catalysts, metallic copper is the most studied one, which can effectively lower the reaction energy barrier and is effective against CO 2 Has high catalytic activity. And the copper catalyst electrochemically reduces CO 2 The low product selectivity and easy catalyst deactivation hinder the practical application of Cu-based catalysts. To address these problematic issues and improve the activity and selectivity of electrocatalysts, the most central challenge is to rationally design electrocatalysts to achieve high efficiency, high selectivity, high stability and low cost.
The carbon aerogel material has an ultrahigh specific surface area and abundant three-dimensional pore structures, and ions and molecules can rapidly enter and diffuse through the three-dimensional interconnected network structures, so that the conductivity of the catalyst is increased, and the carbon aerogel material is a good electrode material of a catalyst carrier, a battery and a super capacitor and is widely applied to the field of catalysis. The traditional preparation methods of the carbon aerogel dispersed copper nanoparticles comprise a direct carbonization method, an activation method and a hydrothermal method, generally utilize the condensation polymerization reaction of phenolic organic matters (such as resorcinol) and aldehydes (formaldehyde), and form a carbon skeleton through solidification, aging, freeze drying and carbonization.
In recent years, biomass carbon aerogel is receiving attention due to environmental protection and low cost. Compared with other biomasses, the silk fibroin contains abundant amino acids such as glycine, alanine, serine and the like, researchers take the silk fibroin as a template agent and a reducing agent, and prepare metal (copper, silver, gold and the like) nano materials by using a hydrothermal method, a low-temperature synthesis method and the like, and the metal nano materials are used in the fields of sewage treatment, sensors and the like. However, the metal nano-material prepared by the methods is embedded in the silk fibroin glue, has poor conductivity, and aims to improve and expand the application of the silk fibroin-based metal material in electrocatalysis, particularly in electrochemical reduction of CO 2 In the field of application, a new method for preparing the catalyst with high conductivity, good stability and uniformly dispersed copper nanoparticles needs to be developed.
Disclosure of Invention
The invention aims to provide a method for preparing silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles, which has the advantages of low cost, simple process and environmental protection. Extracting silk fibroin from natural silkworm cocoon by using CO 2 And uniformly dispersing the metal salt in the silk fibroin solution in a bubbling mode, and performing freeze drying and high-temperature carbonization to obtain the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles. The invention can effectively utilize hetero atoms (nitrogen) in silk fibroin to fix metal ions, realize the high-efficiency dispersion and size control of metal copper ions, and the three-dimensional carbon aerogel substrate is beneficial to CO 2 The mass transfer and the diffusion of reaction intermediates can effectively stabilize the copper nanoparticles, overcome the defects of easy inactivation and poor stability of the traditional copper-based material and obtain the CO with electrocatalytic reduction 2 An active composite material.
The invention provides a preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles, which comprises the following steps:
(1) Extracting the silk fibroin liquid: boiling natural silkworm cocoon in sodium carbonate solution, degumming to obtain silk fiber, washing silk fiber with pure water to remove small molecular substances on surface, drying silk fiber, dissolving dried silk fiber with LiBr until the silk fiber is completely dissolved to obtain silk fibroin solution, dialyzing with dialysis bag in pure water to remove Li + 、Br - And (4) performing particle separation, and finally performing centrifugal treatment on the protein liquid, collecting supernatant, and storing at low temperature for later use.
(2) Preparation of the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticle composite material:
preparing a solution containing copper salt and zinc salt with a certain concentration, adding the fibroin solution obtained in the step (1), and using the solution with a certain flow rateCO 2 Bubbling gas for a period of time to uniformly disperse the metal salt in the protein solution, freeze-drying at a certain temperature for a period of time, and then carrying out N 2 Calcining at high temperature in the atmosphere to obtain the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles.
In the step (2), the mass ratio of the zinc salt to the copper salt to the protein solution is 1:1 to 3:50 to 80.
In step (2), the CO 2 The gas flow rate of (a) is 5mL/min-30mL/min;
in the step (2), the CO 2 The bubbling time is 1h-3h.
In the step (2), the freeze drying temperature is-40 to-60 ℃, and the drying time is 36 to 48 hours.
In the step (2), the calcining temperature is 950 ℃, and the calcining heat preservation time is 2-4h.
The silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles prepared by the method can be used for electrocatalytic reduction of CO 2 The catalyst of (4) and its electrocatalytic properties are discussed.
Compared with the prior art, the method of the invention has the following characteristics:
(1) The silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticle composite material is low in cost, simple in process, green and environment-friendly and capable of uniformly dispersing copper nanoparticles.
(2) The particle size of the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles prepared by the method is 2-5 nm, and the particles are uniformly dispersed in the whole carbon substrate.
(3) The silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles prepared by the method are used for electrochemically reducing CO 2 The catalyst shows better activity in the process, the Faraday efficiency on CO is up to more than 80%, and the catalyst has good stability which is up to 10 hours.
Drawings
FIG. 1 is an XRD pattern of Cu-N-C-1 prepared in example 1.
FIG. 2 is an SEM image and an EDS mapping image of Cu-N-C-2 prepared in example 2.
FIG. 3 is a TEM image of Cu-N-C-3 prepared in example 3.
FIG. 4 shows the electrochemical reduction of CO by Cu-N-C-1 prepared in example 1 2 The product profile of (a).
FIG. 5 is the electrochemical reduction of CO by Cu-N-C-2 prepared in example 2 2 Stability test chart of (1).
The specific implementation mode is as follows:
example 1:
the preparation method of the silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticle composite material comprises the following steps:
at room temperature, 0.6g of copper nitrate and 0.2g of zinc nitrate were dissolved in 10mL of water, 10g of fibroin solution was added, and CO was bubbled at a flow rate of 5mL/min 2 And obtaining a silk fibroin-based nitrogen-doped carbon aerogel dispersed copper nanoparticle precursor after 1h of gas. The obtained precursor was freeze-dried at-40 ℃ for 36h. The obtained precursor was freeze-dried. Finally, it is placed in N 2 Keeping the temperature for 4h at 950 ℃ in the atmosphere. The final product is labeled as Cu-N-C-1.
Example 2:
at room temperature, 0.4g of copper nitrate and 0.4g of zinc nitrate were dissolved in 10mL of water, then 16g of fibroin solution was added, and CO was bubbled at a flow rate of 30mL/min 2 And (3) gas is used for 3h to obtain a silk fibroin-based nitrogen-doped carbon aerogel dispersed copper nanoparticle precursor, and the obtained precursor is frozen and dried for 48h at the temperature of-60 ℃. Finally, it is placed in N 2 Keeping the temperature for 2h at 950 ℃ in the atmosphere. The final product is labeled as Cu-N-C-2.
Example 3:
at room temperature, 0.5g of copper nitrate and 0.4g of zinc nitrate were dissolved in 10mL of water, 13g of fibroin solution was added, and CO was bubbled at a flow rate of 15mL/min 2 And (3) obtaining a silk fibroin-based nitrogen-doped carbon aerogel dispersed copper nanoparticle precursor after 2h of gas, and freeze-drying the obtained precursor at the temperature of-56 ℃ for 40h. Finally, it is placed in N 2 Keeping the temperature for 3h at 950 ℃ in the atmosphere. The final product was labeled Cu-N-C-3.
Example 4
(1) Weighing 5mg of the Cu-N-C-1 sample in example 1, adding 63 mu L of ethanol, 88 mu L of DMF and 20 mu L of Nafion solution, performing ultrasonic treatment for 1h to form a uniform solution, and dropping 20 mu L of the solution on 1cm by 1cm carbon paper;
(2) Using Ag/AgCl as reference electrode and platinum electrode as counter electrode, passing through CO 2 Saturated 0.1mol/L NaHCO 3 The solution is electrolyte, and 20mL/min of CO is continuously introduced in the whole process 2 A gas;
(3) Testing of Cu-N-C-1 electrocatalytic reduction of CO in an H-cell using an electrochemical workstation 2 Electrochemical performance of (3), gas chromatography 1 H nuclear magnetic resonance spectroscopy (NMR) quantitative test, analysis of Cu-N-C-1 electrochemical reduction of CO 2 The product of (1).
Example 5
The electrode preparation procedure was repeated, and the sample of example 2 was weighed and tested for electrochemical reduction of CO under the same conditions 2 Stability of (2).
FIG. 1 is an XRD pattern of Cu-N-C-1, in which peaks at positions of 43.31 degrees, 50.45 degrees and 74.12 degrees of 2 theta values are respectively crystal faces (JCPDS 85-1326) of Cu (111), cu (200) and Cu (220), and characteristic peaks of Zn do not appear, which indicates that the added zinc salt is only used as a pore-forming agent in the preparation process, and the XRD pattern shows that copper nanoparticles are successfully prepared;
from the SEM image and the element distribution diagram of FIG. 2, cu-N-C-2 is a porous carbon structure, and three elements of Cu, N and C are uniformly dispersed in the whole carbon structure;
FIG. 3 is a TEM image of Cu-N-C-3, from which it can be seen that the copper nanoparticles have a particle size of about 2nm to 5nm and are uniformly distributed throughout the carbon structure;
FIG. 4 is a product distribution diagram of Cu-N-C-1 as a catalyst for electrochemical reduction of carbon dioxide, and shows excellent catalytic activity for electrochemical reduction of carbon dioxide, with faradaic efficiency of up to 80% for CO at-1.26V;
FIG. 5 is a stability curve of Cu-N-C-2 electrochemical reduction of carbon dioxide, from which it can be seen that the current density is stabilized at-11.21 mA/cm within the test range of 10h 2 The left and right have smaller fluctuation, which shows that the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nano-particle prepared by the invention has electrochemistryThe stability is better.

Claims (8)

1. A preparation method of silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles is characterized by comprising the following steps:
(1) Extracting fibroin protein solution for later use;
boiling natural silkworm cocoon in sodium carbonate solution, degumming to obtain silk fiber, washing silk fiber with pure water to remove small molecular substances on surface, drying silk fiber, dissolving dried silk fiber with LiBr until the silk fiber is completely dissolved to obtain silk fibroin solution, dialyzing with dialysis bag in pure water to remove Li + 、Br - And finally, centrifuging the protein liquid, collecting supernatant, and storing at low temperature for later use;
(2) Preparation of the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticle composite material:
preparing a solution containing copper salt and zinc salt with a certain concentration, adding the fibroin protein solution obtained in the step (1), and using CO with a certain flow rate 2 Bubbling gas for a period of time to uniformly disperse the metal salt in the protein solution, freeze-drying at a certain temperature for a period of time, and then carrying out N 2 Calcining at high temperature in the atmosphere to obtain the silk fibroin-based nitrogen-doped/porous carbon aerogel dispersed copper nanoparticles.
2. The method for preparing the silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles according to claim 1, wherein in the step (2), the mass ratio of the zinc salt to the copper salt to the protein liquid is 1:1 to 3:50 to 80.
3. The method for preparing silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles according to claim 1, wherein in the step (2), the CO is added 2 The gas flow rate of (2) is 5mL/min to 30mL/min.
4. The method for preparing the silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles as claimed in claim 1, wherein the method comprises the steps ofIn the step (2), the CO 2 The bubbling time is 1h-3h.
5. The preparation method of the silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles as claimed in claim 1, wherein in the step (2), the freeze-drying temperature is-40 to-60 ℃, and the drying time is 36 to 48 hours.
6. The method for preparing the silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles as claimed in claim 1, wherein in the step (2), the calcination temperature is 950 ℃ and the calcination heat preservation time is 2-4h.
7. A silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticle is characterized by being prepared by the preparation method of any one of claims 1 to 6, wherein the particle size of the copper nanoparticle is 2-5 nm, and three elements of Cu, N and C are uniformly dispersed in the whole carbon structure.
8. Use of the silk fibroin-based nitrogen-doped/porous carbon aerogel/copper nanoparticles of claim 7 for electrocatalytic reduction of CO 2 The use of (1).
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