CN109778225B - N, S co-doped graphene/molybdenum selenide/CoFe-LDH aerogel and preparation thereof - Google Patents
N, S co-doped graphene/molybdenum selenide/CoFe-LDH aerogel and preparation thereof Download PDFInfo
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Abstract
The invention provides N, S co-doped graphene/MoSe2The preparation method of the/CoFe-LDH aerogel is characterized by comprising the following steps: s1, respectively preparing graphene oxide lamellar dispersion liquid and MoSe2A nanosheet dispersion and a layered CoFe-LDH nanosheet dispersion; s2, mixing the graphene oxide lamellar dispersion liquid and MoSe2Mixing the nanosheet dispersion liquid, adding a reducing agent and a cross-linking agent, uniformly mixing, and reacting to obtain N, S co-doped graphene/MoSe2Hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2An aerogel; s3, co-doping the N and S with graphene/MoSe2Soaking aerogel in layered CoFe-LDH nanosheet dispersion liquid to prepare N, S co-doped graphene/MoSe2the/CoFe-LDH hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2A/CoFe-LDH aerogel. Ternary N, S co-doped graphene/MoSe prepared by adopting method2the/CoFe-LDH aerogel has more excellent hydrogen and oxygen evolution performances under alkaline conditions.
Description
Technical Field
The invention relates to an electrode hydrogen evolution and oxygen evolution material, in particular to an N, S co-doped graphene/MoSe material2/CoFe-LDH and a preparation method thereof.
Background
Energy and environment are the material bases on which human society lives and develops, and the importance of the energy and the environment is self-evident. In recent years, with the rapid increase of the world population, the accelerated consumption of energy causes the problems of energy shortage, environmental pollution and the like to become more serious, and great threats are caused to the survival and health of human beings. In view of this, the demand for new, sustainable clean energy is urgent. Electrocatalytic water decomposition is one of important ways for efficiently generating renewable clean energy, and the decomposition product of the electrocatalytic water decomposition is only O2And H2Zero environmental pollution, and O2And H2And can be used as the raw material of the fuel cell, so that the water decomposition can ensure the green and environmental protection of the energy utilization process. However, in the process from water electrolysis to hydrogen energy utilization, how to save energy consumption, reduce cost and improve water decomposition efficiency and yield to the maximum extent is a technical problem troubling researchers. The electrolysis reaction of water consists of two half-reactions of Oxygen Evolution (OER) and Hydrogen Evolution (HER), which is crucial to reduce the energy barrier of the half-reactions and improve the energy conversion efficiency. Although noble metal catalysts (such as Pt-based catalysts for hydrogen evolution reaction and Ir-based catalysts for oxygen evolution reaction) are currently the most promising catalysts for water decomposition, their high price and resource scarcity greatly limit their wide use. In recent years, a great deal of research reports that non-noble metal catalysts catalyze the decomposition of water to generate hydrogen or oxygen, and certain progress is made, but the catalysts catalyze the oxygen generation reaction in an alkaline electrolyte or catalyze the hydrogen generation reaction in an acidic electrolyte, and the utilization efficiency of water is not high. Considering the practical application of water splitting, an efficient electrocatalyst must catalyze both hydrogen evolution and oxygen evolution reactions in the same electrolyte (mainly in alkaline electrolytes), which remains a challenge for many current catalysts with high activity in acidic electrolytes. Therefore, research and development of novel and efficient electrocatalysts capable of catalyzing hydrogen evolution reaction and oxygen evolution reaction simultaneously have become the key of the development of the electrocatalytic water decomposition technology.
Layered Double Hydroxide (LDH) is a Layered material that has a large specific surface area and can be artificially synthesized according to specific functions. LDH has various unique physical and chemical properties including laminate electropositivity, host element variability, interlayer spacing adjustability and the like, and therefore has great application potential in the aspects of catalysis, energy sources, water treatment and the like. In recent years, with the continuous and deep research on the structure and the performance of LDH, the materials are found to show excellent activity in the field of electrocatalytic water decomposition. Xiang et al directly grow ZnCo-LDH films on flexible Ni foil substrates at room temperature using electrodeposition, which contain oriented nanowall structures, and show excellent catalytic activity and durability against hydrolytic oxygen evolution reactions under alkaline conditions. The key factor of high activity is that the interconnected two-dimensional LDH nano-sheets are vertically grown on a conductive substrate, so that active sites which are beneficial to catalytic reaction are exposed in a large amount. NiFe-LDH prepared by Li design is an ultrathin nanosheet obtained by inserting molybdate ions. The current density of the material in the alkaline condition for electrocatalytic water decomposition oxygen analysis reaction is 3 times higher than that of the common NiFe-LDH, mainly because the ultrathin thickness is beneficial to fully utilizing the electrochemical active sites, and the catalytic performance is further improved.
Transition metal disulfide (molybdenum disulfide (MoS)2) Molybdenum diselenide (MoSe)2) Due to their unique physical and chemical properties) are also considered to be the most promising class of catalysts for electrocatalytic water-splitting hydrogen analysis reactions. As is known, layered transition metal disulfide can be stripped into a two-dimensional ultrathin nanosheet layer with a graphene-like structure, and the two-dimensional nanosheet layer has a large number of active edge sites, so that the improvement of the reaction performance of the two-dimensional ultrathin nanosheet layer in the electrocatalytic hydrogen decomposition is facilitated. Ultrathin MoS prepared by Cheng et al by high temperature liquid phase synthesis2The nanoplatelets have a thickness of a monoatomic layer and a large number of edge sites, such that the MoS2The nanosheet shows excellent hydrogen evolution reaction catalytic activity in an acidic electrolyte and has good stability. Fu et al on SiO by chemical vapor deposition2Preparation of single-layer MoS on a/Si substrate2(1-x)Se2xMoS of such a single crystal structure2(1-x)Se2xBandgap ofCan be adjusted by changing the proportion of Se and S, so that the activity of the electrocatalytic hydrogen evolution reaction reaches the optimum, and the performance of the catalyst is superior to that of pure monolayer MoS2And MoSe2。
Due to the ultrahigh conductivity, high specific surface area, excellent chemical and environmental stability and strong adsorption, graphene can be used as an excellent catalyst carrier. Research on self-assembly of graphene into three-dimensional graphene hydrogel is widely regarded, and the method is particularly applied to the fields of electrocatalytic water decomposition and the like.
Disclosure of Invention
One of the purposes of the invention is to co-dope the N and S with the graphene/MoSe2/CoFe-LDH and a preparation method thereof.
In order to achieve the purpose, the invention provides N, S co-doped graphene/MoSe2The preparation method of the/CoFe-LDH aerogel is characterized by comprising the following steps:
s1, respectively preparing graphene oxide lamellar dispersion liquid and MoSe2A nanosheet dispersion and a layered CoFe-LDH nanosheet dispersion;
s2, mixing the graphene oxide lamellar dispersion liquid and MoSe2Mixing the nanosheet dispersion liquid, adding a reducing agent and a cross-linking agent, uniformly mixing, and reacting to obtain N, S co-doped graphene/MoSe2Hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2An aerogel;
s3, co-doping the N and S with graphene/MoSe2Soaking aerogel in layered CoFe-LDH nanosheet dispersion liquid to prepare N, S co-doped graphene/MoSe2the/CoFe-LDH hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2A/CoFe-LDH aerogel.
The graphene oxide lamellar dispersion liquid of S1 and MoSe2The preparation of the nano-sheet dispersion liquid and the layered CoFe-LDH nano-sheet dispersion liquid has no sequence, and the sequence can be randomly changed.
Further, the preparation of the graphene oxide lamellar dispersion liquid comprises the step of ultrasonically dispersing graphite oxide in deionized water to prepare the graphene oxide lamellar dispersion liquid.
Further, the MoSe2The nanosheet dispersion was prepared by a liquid phase exfoliation method.
Further, the layered CoFe-LDH nanosheet dispersion is prepared by a hydrothermal method.
Further, the graphite oxide is prepared by the following method:
s11, adding NaNO under ice bath and vigorous stirring3Adding into concentrated sulfuric acid until NaNO3Completely dissolving;
s12, maintaining ice bath, adding graphite powder, and then adding KMnO in batches4After the addition, removing the ice bath, and reacting until the reaction solution is viscous;
s13, adding a first weight of deionized water, reacting for a period of time, and adding a second weight of deionized water at a temperature lower than 120 ℃;
s14, adding H at room temperature2O2Water solution, after the reaction is finished, centrifuging to remove supernatant, and keeping precipitate;
and S15, washing the precipitate with HCl solution, and drying to obtain graphite oxide.
Further, the preparation of MoSe by a liquid phase exfoliation method2The specific steps of the nanosheet dispersion include: adding molybdenum diselenide into the isopropanol/water mixed solution, and performing ultrasonic oscillation to obtain MoSe2A nanosheet dispersion.
Further, the specific steps of preparing the layered CoFe-LDH nanosheet dispersion by a hydrothermal method comprise:
s31, mixing Co (NO)3)2·6H2O、Fe(NO3)3·9H2Dispersing O, urea and trisodium citrate in water, reacting at the temperature of 130-170 ℃, washing and drying after the reaction to obtain a powdery substance;
s32, dispersing the powdery substance in the step S31 in formamide solution, and taking the supernatant as the CoFe-LDH nanosheet dispersion liquid.
Further, in step S2, the graphene oxide sheets and the MoSe2The weight ratio of the nano sheets is 4: 9-36: 1.
Further, the air conditioner is provided with a fan,in step S3, N, S codoped graphene/MoSe2The weight ratio of the CoFe-LDH to the CoFe-LDH is 10: 1-1: 10.
Further, the reducing agent is L-cysteine, ascorbic acid, glucose or any mixture thereof.
Further, the cross-linking agent is L-cysteine and/or polypyrrole.
Further, the step S2 is: dispersing the graphene oxide lamellar layer and MoSe2Mixing the nanosheet dispersion liquid, adding a reducing agent and a cross-linking agent, uniformly mixing, and reacting to obtain N, S co-doped graphene/MoSe2Hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2An aerogel.
The invention also provides N, S co-doped graphene/MoSe prepared by the preparation method2A/CoFe-LDH aerogel.
The N, S co-doped graphene/MoSe provided by the invention2the/CoFe-LDH aerogel can be used as an electrocatalytic water decomposition electrode and has excellent electrocatalytic water decomposition performance when the current density is 100mA/cm2When the reaction is carried out, the overpotential of hydrogen evolution reaction is-237 mV, and the overpotential of oxygen evolution is 1.59V; the electrode has extremely high application value of electrolytic water, and particularly has hydrogen evolution and oxygen evolution performances under alkaline conditions.
Compared with the prior art, the invention adopts graphite oxide and MoSe2And preparing ternary N, S codoped graphene/MoSe by using CoFe-LDH2the/CoFe-LDH aerogel has the following beneficial effects:
1) preparation of ultra-thin MoSe by liquid phase stripping method2The nano-sheet dispersion liquid has the advantages of low cost and safe operation.
2) L-cysteine is used as a cross-linking agent to enable graphene sheet layers to be cross-linked with each other to form a 3D network structure, and is also used as an N, S source to dope graphene, and N, S ratio sp is used2C has a greater electronegativity, which increases its conductivity.
3) N and S codoped graphene/MoSe with negative charges through electrostatic action2Preparing ternary N, S codoped graphene/MoSe through self-assembly effect of the ternary N, S codoped graphene/MoSe and CoFe-LDH with positive charges2the/CoFe-LDH aerogel composite material does not need any harsh conditions, has easily-adjusted product structure and small batch difference, and is suitable for large-scale production.
4) Ternary N, S co-doped graphene/MoSe prepared by adopting method2the/CoFe-LDH aerogel has excellent electrocatalytic water decomposition performance, and the current density is 100mA/cm2When the reaction is carried out, the overpotential of hydrogen evolution reaction is-237 mV, and the overpotential of oxygen evolution is 1.59V;
5) ternary N, S co-doped graphene/MoSe prepared by adopting method2the/CoFe-LDH aerogel has more excellent hydrogen and oxygen evolution performances under alkaline conditions.
Drawings
FIG. 1 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2X-ray powder diffraction pattern of/CoFe-LDH aerogel;
FIG. 2 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2Scanning electron micrographs of/CoFe-LDH aerogel;
FIG. 3 is an enlarged view of a portion of the SEM of FIG. 2;
FIG. 4 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2High-resolution transmission electron microscopy of the/CoFe-LDH aerogel;
FIG. 5 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2a/CoFe-LDH aerogel electrode hydrogen evolution LSV polarization curve diagram;
FIG. 6 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2a/CoFe-LDH aerogel electrode hydrogen evolution Tafel slope curve graph;
FIG. 7 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2a/CoFe-LDH aerogel electrode oxygen evolution LSV polarization curve diagram;
FIG. 8 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2a/CoFe-LDH aerogel electrode oxygen evolution Tafel slope curve graph;
FIG. 9 shows N, S co-doped graphene/MoSe according to an embodiment of the invention2Faradaic efficiency curves for hydrogen and oxygen evolution by the/CoFe-LDH aerogel electrode.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The N, S co-doped graphene/MoSe of the preferred embodiment of the invention2A method for preparing/CoFe-LDH, comprising:
s1, ultrasonically dispersing the graphite oxide in deionized water to prepare graphene oxide lamellar dispersion liquid. Preferably, the concentration of the prepared graphene oxide lamellar dispersion liquid is 0.5-3mg mL-1More preferably 2mg mL-1。
Specifically, the graphite oxide is prepared by the following method:
s11, adding NaNO under ice bath and vigorous stirring3Adding into concentrated sulfuric acid until NaNO3And completely dissolving.
For example: adding 98% concentrated sulfuric acid (H) into a three-mouth reaction bottle2SO4) And the reaction flask is placed in an ice-water bath and stirred at the rotating speed of 150rpm, and NaNO is added3And stirring in ice-water bath to dissolve. Wherein, the concentrated sulfuric acid and NaNO3The weight ratio of: 60: 1-100: 1.
S12, maintaining ice bath, adding graphite powder, and then adding KMnO in batches4And after the addition, removing the ice bath, and reacting until the reaction solution is viscous.
For example: maintaining ice water bath constant, adding natural graphite powder, and adding KMnO4Adding slowly in batches, keeping the reaction temperature below 10 deg.C (more preferably below 5 deg.C), and stirring in ice water bath until the temperature does not rise. The ice-water bath was then removed and the reaction flask was placed in a water bath at 25-45 deg.C (more preferably 35 deg.C) to react until the reaction solution had a viscous greenish black color. Wherein: NaNO3Graphite powder and KMnO4The weight ratio of: (0.5-1.5):(1-3):(4-8).
S13, adding a first weight of deionized water, reacting for a period of time, and adding a second weight of deionized water at a temperature below 120 ℃. Preferably, the first weight is 1.5-2.5 times of the volume of the concentrated sulfuric acid, and the second weight is 2-4 times of the volume of the reaction liquid.
For example: adding deionized water with the first weight, controlling the reaction temperature to be lower than 98 ℃, adding deionized water with the weight more than 1.5 times that of the reaction liquid at 98 ℃ after reacting for a period of time under an oil bath.
The reaction liquid is controlled to be in a micro-boiling state, so that the phenomenon that the system releases heat violently and splashes after deionized water is added into a concentrated sulfuric acid system can be avoided, and particularly the system is dangerous after amplification reaction, so that the micro-boiling of the reaction system is safely controlled, and the temperature is not easy to exceed 98 ℃.
S14, slowly adding H at room temperature2O2And (4) after the aqueous solution and the reaction are finished, centrifuging to remove supernatant, and keeping the precipitate.
For example: slowly add 30 wt% H at room temperature2O2Stirring the aqueous solution for a period of time, centrifuging the aqueous solution in a centrifuge after the reaction is finished, pouring out supernatant liquid, and keeping the precipitate.
And S15, washing the precipitate with HCl solution, and drying to obtain graphite oxide.
For example: washing the precipitate with 10 wt% HCl solution, centrifuging for several times, washing with deionized water until the pH of the supernatant is neutral, and drying the precipitate in an oven at 50-90 deg.C to obtain solid graphite oxide.
S2 preparation of ultrathin MoSe by liquid phase stripping method2A nanosheet dispersion.
For example: dispersing block molybdenum diselenide in isopropanol/water mixed solution, and performing ultrasonic oscillation to obtain ultrathin MoSe2A nanosheet dispersion. In one embodiment, bulk molybdenum diselenide is dispersed in isopropanol/water (V/V, 6/4) mixed solution and stripped into ultra-thin molybdenum diselenide (MoSe) by 300W ultrasonic oscillation for 2-4 hours2) A nanosheet dispersion. Preferably, the MoSe is2The concentration of the nano-sheet dispersion liquid is 0.2-1.0mg mL-1(ii) a More preferably 0.5mg mL-1。
The embodiment of the invention adopts a liquid phase stripping method to prepare ultrathin MoSe2The nano-sheet dispersion liquid has low cost and safe operation.
S3, preparing a layered CoFe-LDH nanosheet dispersion liquid by a hydrothermal method; preferably, the concentration of the CoFe-LDH nanosheet dispersion is (0.5-2) mg.ml-1(ii) a More preferably: 1mg.ml-1。
In particular, the amount of the solvent to be used,
s31, mixing Co (NO)3)2·6H2O、Fe(NO3)3·9H2Dispersing O, urea and trisodium citrate in water, reacting at 130-170 ℃, and washing and drying the obtained product after the reaction. More specifically, the weight ratio of (7-12): (1-4): (2-6): 1 Co (NO)3)2·6H2O、Fe(NO3)3·9H2Dispersing O, urea and trisodium citrate in distilled water, performing ultrasonic treatment until the mixture is clear, sealing the mixture in a stainless steel hydrothermal reaction kettle containing a polytetrafluoroethylene substrate, reacting at the temperature of 130-170 ℃, filtering the mixture after the reaction is finished, washing the mixture for multiple times by using water and ethanol, and performing vacuum drying to obtain a powdery substance.
S32, dispersing the powdery substance in the step S31 in formamide solution, and taking the supernatant as the CoFe-LDH nanosheet dispersion liquid. Specifically, dispersing the powdery substance obtained in the step S31 in a degassed formamide solution, performing ultrasonic treatment to obtain a suspension, centrifuging, removing an un-peeled block, and taking the supernatant to obtain a supernatant, namely the CoFe-LDH nanosheet dispersion.
The above steps S1, S2 and S3 are not sequentially divided, and the sequence of the three steps can be changed at will.
S4, mixing the graphene oxide lamellar dispersion liquid and MoSe2Mixing the nanosheet dispersion liquid, adding a reducing agent and a cross-linking agent, uniformly mixing, and reacting to obtain N, S co-doped graphene/MoSe2Hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2An aerogel.
Preferably, the step S4 includes: dispersing the graphene oxide lamellar layer and MoSe2Mixing the nano-sheet dispersion liquid, adding a reducing agent, a cross-linking agent and a pH regulator, and uniformly stirringEvenly reacting to prepare N, S codoped graphene/MoSe2Hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2An aerogel.
Wherein the graphene oxide sheet layer and the MoSe2The weight ratio of the nano sheets is 4: 9-36: 1. The reducing agent is L-cysteine, ascorbic acid, glucose or any mixture thereof. The cross-linking agent is L-cysteine and/or polypyrrole. The pH regulator is ammonia water with the concentration of 25-28 wt%, and the dosage of the pH regulator is 0.05-0.1 time of the volume of the graphene oxide lamellar dispersion liquid.
In the embodiment, the pH value of the solution is adjusted to 9-11 by using a pH adjusting agent, so that the potential of the surface of the graphene oxide lamella is influenced, and the aggregation state of the reduced graphene oxide in the solution is influenced by using the electrostatic repulsion between the graphene oxide lamella. And then the graphene with good reduction degree and dispersion degree can be prepared without a stabilizer.
In a specific embodiment, the reducing agent and the cross-linking agent are both L-cysteine, the L-cysteine is used as the cross-linking agent to cross-link graphene sheets to form a 3D network structure, and the cross-linking agent can also be used as an N, S source to dope graphene, since N, S is sp compared with graphene2C has a greater electronegativity, which increases its conductivity.
S5, co-doping the N and S with graphene/MoSe2Soaking aerogel in CoFe-LDH nanosheet dispersion liquid to prepare N, S co-doped graphene/MoSe2the/CoFe-LDH hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2a/CoFe-LDH aerogel; wherein, N, S codoped graphene/MoSe2The weight ratio of the CoFe-LDH to the CoFe-LDH is 10: 1-1: 10.
When the N and S are codoped with graphene/MoSe after freeze drying2After the nano-particles are added into the CoFe-LDH nanosheet dispersion liquid, the positively charged CoFe-LDH nanosheets are adsorbed to the negatively charged N, S co-doped graphene/MoSe through electrostatic adsorption2Self-assembling to form N, S codoped graphene/MoSe on the surface2the/CoFe-LDH hydrogel composite material is frozen and dried to obtain N, S codoped graphene/MoSe2the/CoFe-LDH composite aerogel.
According to the method, N and S are codoped with graphene and MoSe2And three layered catalytic materials of CoFe-LDH are compounded to prepare N, S codoped graphene/MoSe2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode and has excellent electrocatalytic water decomposition performance, and when the current density is 100mA/cm, as shown in figures 4 and 62When the reaction is carried out, the overpotential of hydrogen evolution reaction is-237 mV, and the overpotential of oxygen evolution is 1.59V; the catalyst has extremely high application value of water electrolysis, particularly hydrogen and oxygen evolution performance under alkaline conditions and service life, and the performance of the catalyst is close to that of commercial noble metal platinum and iridium catalysts. In addition, the N, S co-doped graphene/MoSe provided by the invention2the/CoFe-LDH composite aerogel has very large specific surface area and very good electronic conduction capability due to doping of N and S to graphene.
The graphite oxide in the following specific examples was prepared by the following method:
to a three-neck reaction flask was added 46mL of concentrated sulfuric acid (98% H)2SO4) And the reaction flask is placed in an ice-water bath to be stirred at the rotating speed of 150rpm, and then 1g of NaNO is weighed3Adding into a reaction bottle, and stirring for 10min under ice-water bath until NaNO3Dissolving completely, keeping ice water bath constant, weighing 2g natural graphite powder, weighing 6g KMnO4Slowly adding in batches, keeping the reaction temperature below 5 ℃, and continuously stirring in an ice water bath for 30min after the addition is finished until the temperature does not rise any more. Then removing the ice water bath, placing the reaction bottle in a water bath with the temperature of 35 +/-3 ℃ for reacting for 1 hour, slowly adding 92mL of deionized water, raising the temperature of the reaction system, controlling the temperature not to exceed 98 ℃, reacting for 15 minutes under a 98 ℃ oil bath, adding 300mL of deionized water while the reaction system is hot, removing the oil bath, cooling the temperature of the reaction system to room temperature, adding 10mL of 30% H2O2And (3) continuously stirring the aqueous solution (slowly adding) for reacting for 1 hour, centrifuging the solution by using a centrifuge with the rotating speed of 5000r min < -1 > after the reaction is finished, pouring out the supernatant, reserving the lower-layer precipitate, washing and centrifuging the precipitate by using 10 wt% HCl solution, repeatedly washing and centrifuging the precipitate for 10 times, and finally washing and centrifuging the precipitate by using deionized water until the pH value of the supernatant is neutral. Subjecting the obtained precipitate to a temperature of 80 deg.CDrying in an oven overnight to obtain solid graphite oxide.
Molybdenum diselenide (MoSe) used in the following examples2) From Michelin, purity 99.8%, MDL number MFCD 00049703.
Example 1
N, S co-doped graphene/MoSe2A preparation method of/CoFe-LDH aerogel comprises the following steps:
(1) preparation of Graphene Oxide (GO) lamellar dispersion: dispersing 200mg of the graphite oxide prepared in the step of preparing into 100mL of deionized water, and performing ultrasonic dispersion for 1 hour to obtain a tan GO lamella dispersion liquid, wherein the concentration of GO is 2mg mL-1。
(2) Preparation of ultrathin MoSe by liquid phase stripping method2Preparation of nanosheet dispersion: 20mg of block MoSe2Adding 4mL of Isopropanol (IPA)/water mixed solvent with volume fraction of 60%, placing the mixture into an ultrasonic instrument, performing ultrasonic oscillation treatment for 4 hours at the power of 200W and the frequency of 40kHz, and adding circulating cooling water to keep the temperature controlled at room temperature during ultrasonic treatment. Subsequently, the sonicated solution was centrifuged at 4000rpm for 20 minutes to remove the bulk MoSe not exfoliated at the bottom2Obtaining supernatant which is two-dimensional MoSe2Nanoplatelets tested at a concentration of about 0.5mg mL-1And then standby.
(3) Preparing a layered CoFe-LDH nanosheet dispersion liquid: 0.27g of Co (NO)3)2·6H2O，0.09g Fe(NO3)3·9H2O, 0.12g urea and 0.03g trisodium citrate were dispersed in 75mL distilled water and sonicated for about 30min until clear. The resulting solution was transferred to a stainless steel hydrothermal reaction vessel containing a polytetrafluoroethylene substrate, sealed, and heated at 150 ℃ for 20 hours. After cooling to room temperature, filtering and collecting a solid product, washing the solid product with distilled water and ethanol for multiple times respectively, performing vacuum drying at 60 ℃ for 8 hours to obtain a powdery substance, adding the powdery substance into 50mL of degassed formamide solution (50 wt%) to perform ultrasonic treatment to obtain a suspension, then centrifuging the suspension at 4000rpm for 20 minutes to remove an un-peeled block material, and taking supernatant, namely layered CoFe-LDH nanosheet dispersion with the concentration of 1 mg/mL.
(4) The 5mL graphene oxide lamellar dispersion (2.0mg mL)-1) And 5mL of MoSe2Nanosheet dispersion (0.5mg mL)-1) Mixing, 50mg L-cysteine and 300. mu.L NH3·H2O (25-28 wt%) was gradually added to 5mL GO (2.0mg mL)-1) And 5mL of MoSe2(0.5mg mL-1) Then the mixture is mixed evenly by ultrasonic. The resulting mixed solution was transferred to a stainless steel hydrothermal reaction vessel containing a polytetrafluoroethylene substrate, sealed, and heated at 180 ℃ for 3 hours. Naturally cooling to room temperature to obtain N, S co-doped graphene (N, S-rGO)/MoSe2A hydrogel. Subsequently, N, S-rGO/MoSe2The hydrogel is washed with distilled water for several times, and then is frozen and dried to obtain N, S-rGO/MoSe2An aerogel.
(5) 10mg of N, S co-doped graphene/MoSe2Aerogel was soaked in 10mL of layered CoFe-LDH nanosheet dispersion (1mg mL)-1) Soaking for 24 hours to enable the layered CoFe-LDH nanosheets to be adsorbed on N, S co-doped graphene/MoSe through electrostatic self-assembly2The balance is achieved. After that, the obtained N, S codoped graphene/MoSe2Washing the layered CoFe-LDH composite hydrogel with distilled water for several times, and then freeze-drying to obtain the N, S co-doped graphene/MoSe2Layered CoFe-LDH aerogels. FIG. 1 shows N, S codoped graphene/MoSe2X-ray powder diffraction pattern of/CoFe-LDH aerogel.
And (3) performance testing:
the prepared N, S co-doped graphene/MoSe2the/CoFe-LDH aerogel is tested by a Scanning Electron Microscope (SEM) and a high-resolution transmission electron microscope. As can be seen from FIG. 2, the prepared N, S co-doped graphene/MoSe2the/CoFe-LDH aerogel forms a 3D pore channel structure, and N and S co-doped graphene/MoSe pore channels2the/CoFe-LDH aerogel, and as can be seen from figures 3 and 4, N and S are codoped with graphene and MoSe2And three basic materials of CoFe-LDH are effectively compounded to form a stable ternary composite material.
FIG. 5 shows N, S codoped graphene/MoSe2Hydrogen evolution LSV polarization curve of/CoFe-LDH aerogel electrode, ternary composite material utensilThe hydrogen evolution performance is excellent, and the smaller the over potential is, the more negative the current density is, which shows that the hydrogen evolution performance is better.
FIG. 6 shows N, S codoped graphene/MoSe2The slope curve diagram of hydrogen evolution Tafel of a/CoFe-LDH aerogel electrode is shown in FIG. 6, and N and S co-doped graphene/MoSe2The hydrogen evolution performance of the/CoFe-LDH aerogel is excellent, and the smaller the slope of the curve is, the better the performance is.
FIG. 7 shows N, S codoped graphene/MoSe2Oxygen evolution LSV polarization curve of/CoFe-LDH aerogel electrode. As can be seen from FIG. 7, N, S codoped graphene/MoSe2the/CoFe-LDH aerogel has excellent oxygen evolution performance, and the smaller the overvoltage is, the higher the current density is, which shows that the oxygen evolution performance is better.
FIG. 8 shows N, S codoped graphene/MoSe2a/CoFe-LDH aerogel electrode oxygen evolution Tafel slope curve graph. As can be seen from FIG. 8, N, S codoped graphene/MoSe2The oxygen evolution performance of the/CoFe-LDH aerogel is excellent, and the smaller the slope of the curve is, the better the performance is.
FIG. 9 is N, S codoped graphene/MoSe2Faradaic efficiency curves for hydrogen and oxygen evolution by the/CoFe-LDH aerogel electrode. As can be seen from FIG. 9, N, S codoped graphene/MoSe2The actual hydrogen and oxygen evolution efficiency of the/CoFe-LDH aerogel is close to the theoretical value.
Example 2
The reaction and operation conditions of this example are substantially the same as those of example 1, except that the reducing agent in example 1 is ascorbic acid and the crosslinking agent is polypyrrole.
Tests show that the composite aerogel prepared by the invention has excellent electrocatalytic water decomposition performance when being used as an electrocatalytic water decomposition electrode, and the current density is 100mA/cm as shown in figures 5-82The overpotential for the hydrogen evolution reaction was-290 mV and the overpotential for the oxygen evolution reaction was 1.65V.
Example 3
The reaction and operation conditions of this example are substantially the same as those of example 1, except that the reducing agent in example 1 is replaced with glucose and the crosslinking agent is polypyrrole.
The composite aerogel prepared by the invention is obtained by testingAs an electrocatalytic water-splitting electrode, it has excellent electrocatalytic water-splitting performance, as shown in FIGS. 5 to 8, when the current density is 100mA/cm2The overpotential for the hydrogen evolution reaction is-271 mV, and the overpotential for the oxygen evolution reaction is 1.84V.
Example 4
The reaction and operation conditions of this example are substantially the same as those of example 1, except that the crosslinking agent in example 1 is replaced with polypyrrole and the reducing agent is polypyrrole.
Tests show that the composite aerogel prepared by the invention has excellent electrocatalytic water decomposition performance when being used as an electrocatalytic water decomposition electrode, and the current density is 100mA/cm as shown in figures 5-82When the reaction is carried out, the overpotential for the hydrogen evolution reaction is-349 mV, and the overpotential for the oxygen evolution reaction is 1.93V.
Example 5
This example was conducted under substantially the same reaction and operating conditions as example 1, except that the GO dispersion had a concentration of 3mg/mL and MoSe2The concentration of the nanosheet dispersion was 1 mg/mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2When the reaction is carried out, the overpotential for the hydrogen evolution reaction is-317 mV, and the overpotential for the oxygen evolution reaction is 1.63V
Example 6
The reaction and operating conditions of this example were essentially the same as those of example 1, except that the concentration of the GO dispersion was 0.5mg/mL and the concentration of the layered CoFe-LDH nanosheet dispersion was 0.5 mg/mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2The overpotential for the hydrogen evolution reaction was-417 mV and the overpotential for the oxygen evolution reaction was 1.64V.
Example 7
This example is essentially the same as example 1 with respect to the reaction and operating conditions, except that the GO dispersion is(concentration 2.0mg/mL) volume 1mL, MoSe2The volume of the nanoplatelet dispersion (0.5mg/mL) was 9 mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2When the reaction is carried out, the overpotential of the hydrogen evolution reaction is-369 mV, and the overpotential of the oxygen evolution reaction is 1.78V.
Example 8
This example is essentially the same as example 1 except that the volume of GO (2.0mg/mL) dispersion is 1mL and the MoSe is present2The concentration of the nanosheet dispersion was 0.2mg/mL, and the volume was 6 mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2When the reaction is carried out, the overpotential for the hydrogen evolution reaction is-359 mV, and the overpotential for the oxygen evolution reaction is 1.83V.
Example 9
This example is essentially the same as example 1 except that the volume of GO (2.0mg/mL) dispersion is 1mL and the MoSe is present2The volume of the nanoplatelet dispersion (0.5mg/mL) was 3 mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2The overpotential for the hydrogen evolution reaction was-324 mV and the overpotential for the oxygen evolution reaction was 1.75V.
Example 10
This example is essentially the same as example 1 except that the volume of GO (2.0mg/mL) dispersion is 3mL and the MoSe is present2The volume of the nanoplatelet dispersion (0.5mg/mL) was 1 mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode and has excellent electrocatalytic performanceThe water decomposition performance is improved when the current density is 100mA/cm2When the reaction is carried out, the overpotential of the hydrogen evolution reaction is-316 mV, and the overpotential of the oxygen evolution reaction is 1.98V.
Example 11
This example is essentially the same as example 1 except that the volume of GO (2.0mg/mL) dispersion is 6mL and the MoSe is present2The volume of the nanoplatelet dispersion (0.5mg/mL) was 1 mL.
Example 12
This example is essentially the same as example 1 except that the volume of GO (2.0mg/mL) dispersion is 9mL and the MoSe is present2The volume of the nanosheet dispersion (0.5mg/mL) was 1mL, and the concentration of the CoFe-LDH nanosheet dispersion was 2 mg/mL.
Through testing, the N, S co-doped graphene/MoSe prepared by the invention2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2The overpotential for the hydrogen evolution reaction is-379 mV and the overpotential for the oxygen evolution reaction is 1.86V.
The foregoing is only a partial embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (2)
1. N, S co-doped graphene/MoSe2The preparation method of the/CoFe-LDH aerogel is characterized by comprising the following steps:
s1, respectively preparing graphene oxide lamellar dispersion liquid and MoSe2A nanosheet dispersion and a layered CoFe-LDH nanosheet dispersion; the preparation of the graphene oxide lamellar dispersion liquid comprises the steps of ultrasonically dispersing graphite oxide in deionized water to prepare the graphene oxide lamellar dispersion liquid; the graphite oxide is prepared by the following method:
s11, adding NaNO under ice bath and vigorous stirring3Adding into concentrated sulfuric acid until NaNO3Completely dissolving;
s12, maintaining ice bath, adding graphite powder, and then adding KMnO in batches4After the addition, removing the ice bath, and reacting until the reaction solution is viscous;
s13, adding a first weight of deionized water, reacting for a period of time, and adding a second weight of deionized water at a temperature lower than 120 ℃;
s14, adding H at room temperature2O2Water solution, after the reaction is finished, centrifuging to remove supernatant, and keeping precipitate;
s15, washing the precipitate with HCl solution, and drying to obtain graphite oxide;
preparation of MoSe by liquid phase exfoliation2The specific steps of the nanosheet dispersion include: adding molybdenum diselenide into the isopropanol/water mixed solution, and performing ultrasonic oscillation to obtain MoSe2A nanosheet dispersion;
the preparation method of the layered CoFe-LDH nanosheet dispersion by a hydrothermal method comprises the following specific steps:
s31, mixing Co (NO)3)2·6H2O、Fe(NO3)3·9H2Dispersing O, urea and trisodium citrate in water, reacting at the temperature of 130-170 ℃, washing and drying after the reaction to obtain a powdery substance;
s32, dispersing the powdery substance in the step S31 in formamide solution, and taking supernatant as CoFe-LDH nanosheet dispersion liquid;
s2, mixing the graphene oxide lamellar dispersion liquid and MoSe2Mixing the nanosheet dispersion liquid, adding a reducing agent and a cross-linking agent, uniformly mixing, and reacting to obtain N, S co-doped graphene/MoSe2Hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2An aerogel; the graphene oxide sheet layer and the MoSe2The weight ratio of the nano sheets is 4: 9-36: 1; the reducing agent is L-cysteine; the cross-linking agent is L-cysteine;
s3, co-doping the N and S with graphene/MoSe2Soaking aerogel in layered CoFe-LDH nanosheet dispersion liquid to prepare N, S co-doped graphene/MoSe2the/CoFe-LDH hydrogel is frozen and dried to obtain N, S codoped graphene/MoSe2a/CoFe-LDH aerogel; co-doping of N, Sgraphene/MoSe2The weight ratio of the CoFe-LDH to the CoFe-LDH is 10: 1-1: 10;
s4, co-doping N and S with graphene and MoSe2And three layered catalytic materials of CoFe-LDH are compounded to prepare N, S codoped graphene/MoSe2the/CoFe-LDH composite aerogel is used as an electrocatalytic water decomposition electrode, has excellent electrocatalytic water decomposition performance, and has a current density of 100mA/cm2When the reaction is carried out, the overpotential for hydrogen evolution reaction is-237 mV, and the overpotential for oxygen evolution is 1.59V.
2. N, S-codoped graphene/MoSe prepared by the preparation method of claim 12A/CoFe-LDH aerogel.
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