CN112076763B - Ni/Ni3S2Nanocluster-graphene composite material and preparation method and application thereof - Google Patents
Ni/Ni3S2Nanocluster-graphene composite material and preparation method and application thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/33—Electric or magnetic properties
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
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Abstract
The invention discloses Ni/Ni3S2A nano-cluster-graphene composite material, a preparation method thereof and application thereof in electrocatalytic oxygen evolution. CdS nanoparticles are accumulated on cell membranes by changing the components of a culture medium to regulate and control bacteria (Pandoraea sp.B-6, with the preservation number of CGMCC No.4239), and Graphene Oxide (GO) and Ni are sequentially loaded on the cell membranes by taking the CdS nanoparticles as carriers through electrostatic adsorption2+To form a composite precursor, and then preparing the catalyst by one-step pyrolysis, wherein the preparation method is simple, convenient, safe, cheap and easy to control. The material has excellent OER catalytic activity, low reaction energy barrier, more active sites and higher electrochemical active surface area, the electron transfer efficiency is improved due to the advantageous conductivity, high catalytic performance and high stability can be maintained in a long-time catalytic process, and the material can replace noble metals to promote the development of an electrolytic water system in an alkaline medium.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and particularly relates to Ni/Ni3S2A nano-cluster-graphene composite material, a preparation method thereof and application thereof in electrocatalytic oxygen evolution.
Background
The ever-increasing global energy consumption requires a sustainable energy supply. Water splitting devices triggered by Oxygen Evolution Reactions (OERs) and Hydrogen Evolution Reactions (HERs) are highly considered to be ideal next generation energy storage or conversion technologies. The complex four electron transfer process inherent to OER has always been the biggest limitation to improve overall water splitting efficiency compared to HER. To accelerate this complex process, there is an urgent need to develop efficient, stable OER electrocatalysts. To date, it has been recognized that the most effective, stable OER catalysts remain based on noble metal oxides, such as IrO, in acidic or basic media2And RuO2. However, the high cost and scarcity of highly active noble metal-based catalysts severely hamper their large-scale application.
Currently, efforts are underway to explore earth-rich non-noble metal electrocatalysts, particularly supported transition metal catalysts such as first row (3d) transition metal oxides, sulfides, selenides, phosphides, and double hydroxides, among others. These catalysts, which can replace precious metals, have attracted increasing interest in the research of renewable energy sources. Among these materials, nickel-based compounds, in particular for nickel sulfide (Ni)3S2) Is considered one of the most widely studied OER catalytic materials due to its promising OER performance and cost effectiveness. Despite good electrochemical performance, the low conductivity and limited number of exposed active sites inherently hinder the improvement of its potential catalytic performance.
In addition, the elemental nickel nanoparticles are also one of the widely studied electrocatalytic materials, however, due to the problems of the structure size, the surface activity and the like, the electrochemical stability is poor, so that the stability is improved by studying common structure coating or heterogeneous compounding, but the prepared elemental nickel composite material is mostly applied to a HER catalyst and rarely relates to an OER system.
Graphene-based electrocatalytic materials that benefit from inherently high surface areas and provide a large number of active centers are considered promising candidates for various energy conversion and storage systems. However, due to the inherently high fermi level of graphene, a high applied voltage is inevitably required to cause the graphene catalyst to activate oxygen intermediates.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide Ni/Ni3S2The nano-cluster-graphene composite material is induced to form ultra-small-sized simple substance Ni and Ni in a pyrolysis process by a biological deposition mediated method, and a preparation method and application thereof3S2The coupled nanoclusters are anchored on a graphene substrate and show high stability and high catalytic activity when applied to OER catalysis.
The invention relates to Ni/Ni3S2The nano-cluster-graphene composite material is composed of a graphene matrix and Ni/Ni uniformly fixed on the graphene matrix3S2And (4) nano-cluster composition.
Preferably, the Ni/Ni3S2Nanoclusters of Ni and Ni3S2Formed by chemical coupling.
Ni/Ni provided by the invention3S2Nanocluster-graphene composite, Ni/Ni3S2Nano-cluster is embedded into the layer of graphene and uniformly fixed on the graphene substrate, and the Ni/Ni3S2The nano cluster is composed of simple substances Ni and Ni3S2The two materials form a composite nano cluster through chemical coupling, and the coupling of a heterogeneous interface causes lattice disorder of the two-phase material to a certain degree, so that more active sites are added. Meanwhile, by introducing 3d transition metal ions as strong electron acceptors, the Fermi level of the graphene is reduced, and the energy difference between the sigma state and the Fermi level of the graphene can be effectively reduced, so that the electron transfer barrier of the graphene is reduced, the conductivity of the material is improved, and the electrocatalysis performance of the composite material is finally improved. In addition, the support of the graphene substrate also enhances the stability of the catalyst.
Preferably, the Ni/Ni3S2The diameter of the nano-cluster is 10 nm-100 nm. In the present invention, Ni/Ni3S2The particle size distribution of the nano-clusters is very uniform, and most of the nano-clusters are about 30nmAnd (4) right.
The invention relates to Ni/Ni3S2The preparation method of the nano-cluster-graphene composite material comprises the following steps:
(1) inoculating bacteria into a Cd-containing sterile culture medium, culturing, and performing solid-liquid separation to obtain a CdS-bacteria precursor;
(2) sequentially loading Graphene Oxide (GO) and Ni on the CdS-bacterial precursor obtained in the step (1) through electrostatic adsorption2+Carrying out solid-liquid separation and drying to obtain a sandwich CdS-bacterium/GO/Ni composite precursor;
(3) putting the CdS-bacterium/GO/Ni composite precursor obtained in the step (2) into a protective atmosphere for pyrolysis treatment, wherein the obtained pyrolysis product is Ni/Ni3S2A nanocluster-graphene composite material.
In step (1) of the present invention, the CdS-bacterial precursor refers to bacteria that accumulate CdS nanoparticles. The biologically deposited CdS is uniformly distributed in the periplasm space of bacterial cell membrane in the form of nano crystals, and on one hand, the CdS is used as a sulfur source to realize Ni2+In situ sulfidation of, in situ synthesized Ni3S2The metal Ni simple substance and the reduced metal Ni simple substance are chemically coupled to form a composite nano cluster to be anchored on graphene, and on the other hand, Cd steam is formed in pyrolysis to form pores so as to optimize the structure of the composite material.
Preferably, the bacteria in step (1) are bacteria having sulfide synthesizing ability.
In the present invention, there is no need for an excessive restriction on the kind of the bacteria in step (1), and for example, bacteria having a sulfide synthesizing ability, such as Pseudomonas, Escherichia coli, and Shewanella, which have been reported in the prior art, can be used.
Preferably, the bacterium is Pandora sp.B-6 with the preservation number of CGMCC No. 4239.
In the present invention, Pandora sp. B-6, which has a collection number of CGMCC No.4239, is a strain which is self-collected by the inventors and published in a published document.
Preferably, in the step (1), the culture condition of the bacteria is that the inoculation amount is 2-10%, the temperature is 25-40 ℃, the natural pH condition is adopted, and the culture time is 20-36 h.
Further preferably, the culture condition of the bacteria is that the inoculation amount is 10%, the temperature is 30 ℃, the natural pH condition is adopted, and the culture time is 24 h.
Preferably, in the step (1), Cd is contained in the Cd-containing sterile medium2+The molar concentration of (B) is 0.2 to 0.5mM, preferably 0.3 to 0.4mM, and more preferably 0.4 mM.
The research shows that Cd in the culture medium2+The concentration significantly affects the growth of bacteria and the accumulation of CdS nanoparticles, thereby affecting the Ni content in the final composite material3S2The content of (a). When Cd2+Bacterial growth was unaffected and accumulated CdS content increased with increasing concentration increasing from 0.2mM to 0.4mM, but Cd2+When the concentration is increased to 0.5mM, the tolerance of the bacteria to Cd is exceeded, so that the growth of the bacteria is influenced2+The bacteria accumulated the highest CdS content at 0.4mM and the final product showed the best electrocatalytic performance.
Preferably, in the step (1), the solid-liquid separation mode is centrifugal separation, the rotation speed of the centrifugal separation is 6500-8500rpm, and the time is 3-10 min.
Preferably, the sterile culture medium containing Cd in the step (1) is a sterile culture medium taking glucose as a unique carbon source, and the components of the sterile culture medium are 2g/L of glucose and Cd (NO)3)2 0.2-0.5mM，NH4Cl1.5 g/L，MgCl2 0.2g/L， CaCl2 0.01g/L，FeSO4·7H2O 0.015g/L，MnSO4·H2O 0.01g/L；MOPs8.314g/L，Tricine 4mM，L-cysteine 0.1mM。
Preferably, in the step (2), the electrostatic adsorption process is as follows: dispersing CdS-bacteria precursor in pure water to obtain dispersion, adding GO solution into the dispersion, performing first adsorption and solid-liquid separation to obtain CdS-bacteria/GO hybrid, and dispersing the CdS-bacteria/GO hybrid in NiCl2And (3) in the solution, performing second adsorption and solid-liquid separation to obtain the CdS-bacterium/GO/Ni composite precursor.
Further preferably, the concentration of CdS-bacterial precursor in the dispersion is OD600 ═ 1.5 to 2.5.
Further preferably, the concentration of GO in the GO solution is 0.3-0.5mg/mL, and the volume ratio of the GO solution to the dispersion liquid is 1: 3-6.
Further preferably, the time for the first adsorption is 30-100 min.
In the actual operation process, the first adsorption process and the second adsorption process are carried out under magnetic stirring, and after the adsorption is finished, a required product is obtained in a centrifugal separation mode. Wherein the speed and time of centrifugation can be set according to conventional techniques, such as centrifugation at 8,000rpm for 5 min.
Further preferably, the NiCl is2In solution, NiCl2The concentration of (A) is 3-6 g/L.
Further preferably, said CdS-bacterium/GO hybrid is mixed with NiCl2The solid-liquid mass volume ratio of the solution is 1-3 g: 100mL
Further preferably, the time of the second adsorption is 2 to 6 hours, preferably 4 hours.
Preferably, the CdS-bacterium/GO/Ni composite precursor obtained in the step (2) is subjected to vacuum freeze drying to constant weight and then is subjected to pyrolysis reaction.
Preferably, in the step (3), the temperature of the pyrolysis treatment is 600-.
Further preferably, the temperature of the high-temperature pyrolysis treatment is 700 ℃, the heating rate is 5 ℃/min, and the heat preservation time is 2 h.
Preferably, in the step (3), the protective atmosphere is a nitrogen atmosphere.
In the pyrolysis reaction, insufficient pyrolysis temperature, too short time and too slow temperature rise all cause insufficient in-situ vulcanization degree of the sample; too high pyrolysis temperature, too long time and too fast temperature rise all can lead to sulfur source loss, product morphology change and the graphene substrate is too thick. The pyrolysis is carried out under the conditions of the invention, so that the in-situ vulcanization effect is better, and the obtained product has better OER performance.
The invention also provides the Ni/Ni3S2Nano meterUse of cluster-graphene composite material, said Ni/Ni3S2The nano-cluster-graphene composite material is used as an OER catalytic electrode material.
Principles and advantages
1. The invention realizes Ni by using nano CdS as sulfur source in the pyrolysis process by using a bacterial deposition-mediated method2+In situ sulfidation of, in situ synthesized Ni3S2Chemically coupled with reduced metal Ni simple substance to form composite nanoclusters anchored on graphene, and Ni/Ni uniformly distributed on graphene substrate is formed3S2A nanocluster composite structure. The uniform distribution and size control of the nanoclusters are ensured through controllable in-situ vulcanization and reduction. Furthermore, Ni3S2Has strong coupling effect with simple substance Ni, forms crystal defects and increases active sites. Due to electronegativity difference, electrons on the metal Ni shift to S to obtain S in an electron-rich state, so that Ni is further optimized3S2The catalytic activity of the graphene oxide catalyst promotes the transmission of electrons from surface active sites to metal Ni in the reaction process, and the good conductivity of the Ni is beneficial to the further conduction of the electrons to a graphene conductive substrate, so that a high-conductivity framework is formed to ensure the electron transfer in the catalytic process, and the catalytic performance is improved.
2. The invention regulates and controls the degree of in-situ vulcanization reaction by regulating the pyrolysis temperature and time, and Cd is obtained in the pyrolysis process2+Is reduced into a Cd simple substance and forms Cd steam to overflow, thereby optimizing a pore system structure and increasing the specific surface area, and further promoting the mass transfer in the catalytic process.
3. Ni/Ni provided by the invention3S2The electrode of the nano-cluster-graphene composite material shows excellent catalytic activity in OER reaction, and the electrochemical test result shows that Ni/Ni3S2When an electrode of the nano-cluster-graphene composite material is subjected to OER reaction under an alkaline condition, only 320mV is needed to realize 100mAcm-2The Tafel slope is as low as 41mVdec-1High intrinsic reaction activity is proved, and simultaneously, the Ni/Ni is proved by 30h of undamped continuous electrolytic oxygen evolution3S2The nano-cluster-graphene composite material has good catalytic stability and applicability.
Drawings
FIG. 1 shows Ni/Ni obtained in example 1 of the present invention3S2Transmission Electron Microscopy (TEM) images of nanocluster-graphene composites.
FIG. 2 shows Ni/Ni obtained in example 1 of the present invention and comparative example 13S2An X-ray diffraction (XRD) pattern of the nanocluster-graphene composite.
FIG. 3 shows Ni/Ni obtained in example 1, comparative example 1 and comparative example 2 of the present invention3S2An electrochemical performance characterization diagram of an OER reaction of the nano-cluster-graphene composite material in a 1MKOH solution;
wherein, (a) is the comparison of OER reaction polarization curves of different composite materials; (b) tafel slope of OER reactions for different composites were compared.
FIG. 4 shows Ni/Ni obtained in example 1 of the present invention3S2And (3) a stability test curve of continuous electrolysis of the electrode of the nano cluster-graphene composite material in a 1MKOH solution.
Detailed Description
The present invention will be described in detail with reference to examples, but the present invention is not limited thereto.
Unless otherwise indicated, the raw materials and reagents used in the following examples are all commercially available products or can be prepared by known methods.
Example 1
This example 1 provides a graphene supported Ni/Ni3S2A method for preparing a nanocluster composite comprising the steps of:
(1) inoculating the Pandoraea sp.B-6 thallus stored on an LB inclined plane into an LB liquid culture medium, and culturing at the temperature of 30 ℃ for 18h to obtain a seed solution of Pandoraea sp.B-6; wherein the LB liquid culture medium comprises the following components in percentage by weight: 10g of peptone, 5g of yeast powder, 10g of sodium chloride and 1L of distilled water; the LB inclined plane is formed by adding 15g/L agar on the basis of the formula;
(2) centrifuging the obtained Pandoraea sp.B-6 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) inoculating the collected Pandoraea sp.B-6 thallus into a Cd-containing sterile culture medium according to the inoculation amount of 10% (the ratio of the volume of the bacterium liquid transferred to the volume of the culture liquid after inoculation), culturing at the temperature of 30 ℃ and natural pH for 24h, and centrifuging at the rotating speed of 8,000rpm for 5min to separate to obtain bacterial thallus; the Cd-containing sterile culture medium comprises the following components in parts by weight: glucose 2g/L, Cd (NO)3)2，0.4mM，NH4Cl1.5 g/L，MgCl2 0.2g/L， CaCl2 0.01g/L，FeSO4·7H2O 0.015g/L，MnSO4·H2O 0.01g/L；MOPs8.314g/L， trineg/L，L-cysteine 0.1mM。
(4) And (3) dispersing the CdS-bacterial precursor obtained in the last step in 200mL of pure water, adjusting the concentration to OD600 to be 2, adding 50mL of GO solution with the concentration of 0.5mg/mL, and magnetically stirring for 30 min. Centrifuging at 8,000rpm for 5min to obtain CdS-bacteria/GO hybrid.
(5) Dispersing the obtained CdS-bacterium/GO hybrid in 100mL NiCl with the concentration of 5g/L according to the solid-to-liquid ratio of 2 percent (2g)2Magnetically stirring the solution for 4h, and centrifuging the solution at 8,000rpm for 5min to obtain the CdS-bacterium/GO/Ni composite precursor.
(6) Carrying out vacuum freeze drying on the obtained CdS-bacterium/GO/Ni composite precursor to constant weight, and carrying out pyrolysis reaction in inert atmosphere to obtain graphene supported Ni/Ni3S2The atmosphere of the pyrolysis treatment is nitrogen atmosphere, the temperature is 700 ℃, the time of carbonization treatment is 2h, and the temperature rise speed is 5 ℃/min;
the TEM result of the catalyst material prepared in this example 1 is shown in fig. 1, the XRD pattern of the catalyst material prepared in example 1 is shown in fig. 2, and the comparison result of the corresponding crystal phases according to XRD shows that the composite material is graphene, metal Ni and Ni3S2The TEM image shows that the material structure is metal Ni and Ni supported by graphene3S2Coupled nano-clusters, the size of the nano-clusters is between 10 and 100nm, the diameter of most nano-clusters is about 30nm, and the distribution is uniform.
The catalytic material and Nafion are dispersed in a mixed solvent of ethanol and pure water, are uniformly mixed by ultrasonic waves, and then are dripped on a glassy carbon electrode (the diameter is 0.4cm) for natural drying to prepare a working electrode, and the electrochemical performance of the working electrode is tested under a three-electrode system (a platinum sheet is used as a counter electrode, a Hg/HgO electrode is used as a reference electrode, and a 1M KOH aqueous solution is used as an electrolyte).
FIG. 3(a) is the polarization curve at a sweep rate of 5mV/s for the electrodes prepared in example 1 and the comparative example, and FIG. 3(b) is the Tafel curve for the electrodes prepared in example 1 and the comparative example, showing that the graphene-supported Ni/Ni synthesis mediated by bioprecipitation is supported3S2Compared with graphene/Ni composite materials without biological effect and graphene/bacteria composite materials without Ni load, the nano-cluster composite materials have remarkable improvement on OER catalytic activity. At 100mAcm-2The overpotential of the catalyst under the large current density is only 320mV, which is superior to most of the prior advanced transition metal OER catalysts. This indicates that the catalysts we prepared benefit from the ultra-small size of Ni/Ni3S2The nanoclusters have excellent catalytic activity as a unit of catalytic activity. Due to the importance of the active area, the oxygen evolution catalyst was evaluated by calculating the electrochemically active surface area (ECSA). Apparently, with the reported Ni2S3Catalyst in contrast, the catalyst synthesized in this example had a density of 15.6mF cm-2Advantageous electrochemically active surface area. Meanwhile, the Tafel slope of the material is 41mV dec-1Much lower than the comparative example, indicating a stronger mass/charge transfer capability. The enhanced OER kinetics are due to improved electron transport and an increase in the number of active surface sites on the in situ generated nanointerfaces.
To examine the OER stability of the catalyst, we measured the OER stability at 100mA cm-2The OER was operated continuously for 30 hours at constant current (fig. 4). The overpotential of the catalyst synthesized in this example remained stable without significant fluctuation during this period. The results show that the graphene supported Ni/Ni3S2The nanocluster composite material has good cycling stability.
In summary, the graphene-supported Ni/Ni of the present invention3S2The in-situ self-growth structure and the interface coupling effect of the nano-cluster composite material endow the nano-cluster composite material with rich OER catalysisThe active site and excellent catalytic stability can efficiently and stably catalyze the OER under low overpotential in the electrochemical reaction process, and has good application prospect.
Example 2
(1) Seed liquid of Pandoraea sp.B-6 was obtained by culturing according to the procedures (1) and (2) of example 1.
(2) Centrifuging the obtained Pandoraea sp.B-6 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) inoculating the collected Pandoraea sp.B-6 thallus into a Cd-containing sterile culture medium according to the inoculation amount of 10% (the ratio of the volume of the bacterium liquid transferred to the volume of the culture liquid after inoculation), culturing at the temperature of 30 ℃ and natural pH for 18h, and centrifuging at the rotating speed of 8,000rpm for 5min to separate to obtain bacterial thallus; the Cd-containing sterile culture medium comprises the following components in parts by weight: glucose 2g/L, Cd (NO)3)2，0.3mM，NH4Cl1.5 g/L，MgCl2 0.2g/L， CaCl2 0.01g/L，FeSO4·7H2O 0.015g/L，MnSO4·H2O 0.01g/L；MOPs8.314g/L， trineg/L，L-cysteine 0.1mM。
(4) And (3) dispersing the CdS-bacterial precursor obtained in the last step in 200mL of pure water, adjusting the concentration to OD600 to be 2, adding 50mL of GO solution with the concentration of 0.5mg/mL, and magnetically stirring for 30 min. Centrifuging at 8,000rpm for 5min to obtain CdS-bacteria/GO hybrid.
(5) Dispersing the obtained CdS-bacterium/GO hybrid in 100mL NiCl with the concentration of 5g/L2Magnetically stirring the solution for 4h, and centrifuging the solution at 8,000rpm for 5min to obtain the CdS-bacterium/GO/Ni composite precursor.
(6) Carrying out vacuum freeze drying on the obtained CdS-bacterium/GO/Ni composite precursor to constant weight, and carrying out pyrolysis reaction in inert atmosphere to obtain graphene supported Ni/Ni3S2The atmosphere of the pyrolysis treatment is nitrogen atmosphere, the temperature is 800 ℃, the time of carbonization treatment is 3h, and the temperature rise speed is 5 ℃/min;
the electrochemical properties were measured in the same manner as in example 1.
Catalyst material obtained in example 2The material is scanned at a rate of 5mV/s at 100mAcm-2Has an overpotential of 350mV and a Tafel slope of 54mVDec-1Exhibits excellent OER catalytic activity and rapid reaction kinetics.
Example 3
(1) Seed liquid of Pandoraea sp.B-6 was obtained by culturing according to the procedures (1) and (2) of example 1.
(2) Centrifuging the obtained Pandoraea sp.B-6 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) inoculating the collected Pandoraea sp.B-6 thallus into a Cd-containing sterile culture medium according to the inoculation amount of 10% (the ratio of the volume of the bacterium liquid transferred to the volume of the culture liquid after inoculation), culturing at the temperature of 30 ℃ and natural pH for 18h, and centrifuging at the rotating speed of 8,000rpm for 5min to separate to obtain bacterial thallus; the Cd-containing sterile culture medium comprises the following components in parts by weight: glucose 2g/L, Cd (NO)3)2，0.4mM，NH4Cl1.5 g/L，MgCl2 0.2g/L， CaCl2 0.01g/L，FeSO4·7H2O 0.015g/L，MnSO4·H2O 0.01g/L；MOPs8.314g/L， trineg/L，L-cysteine 0.1mM。
(4) And (3) dispersing the CdS-bacterial precursor obtained in the last step in 200mL of pure water, adjusting the concentration to OD600 to be 2, adding 50mL of GO solution with the concentration of 0.5mg/mL, and magnetically stirring for 30 min. Centrifuging at 8,000rpm for 5min to obtain CdS-bacteria/GO hybrid.
(5) Dispersing the obtained CdS-bacterium/GO hybrid in 100mL NiCl with the concentration of 5g/L2Magnetically stirring the solution for 4h, and centrifuging the solution at 8,000rpm for 5min to obtain the CdS-bacterium/GO/Ni composite precursor.
(6) Carrying out vacuum freeze drying on the obtained CdS-bacterium/GO/Ni composite precursor to constant weight, and carrying out pyrolysis reaction in inert atmosphere to obtain graphene supported Ni/Ni3S2The atmosphere of the pyrolysis treatment is nitrogen atmosphere, the temperature is 600 ℃, the time of carbonization treatment is 2h, and the temperature rise speed is 3 ℃/min;
the electrochemical properties were measured in the same manner as in example 1.
Go through the bookThe catalyst material prepared in example 3 was scanned at a rate of 5mV/s at 100mA cm-2The overpotential of (1) is 335mV, and the Tafel slopes are 47mV Dec-1。
Comparative example 1
The preparation method of the graphene/Ni composite material related to the comparative example adopts pure electrostatic adsorption synthesis, does not relate to biological action under the condition, and comprises the following specific steps:
(1) 50mL of GO solution with the concentration of 0.5mg/mL is dripped into 100mL of NiCl with the concentration of 5g/L2Magnetically stirring the solution for 4h, and centrifuging at 8,000rpm for 5min to obtain GO/Ni hybrid.
(2) Carrying out vacuum freeze drying on the obtained GO/Ni hybrid to constant weight, and then carrying out pyrolysis reaction in an inert atmosphere to obtain the graphene/Ni composite material, wherein the pyrolysis treatment atmosphere is a nitrogen atmosphere, the temperature is 700 ℃, the carbonization treatment time is 2h, and the temperature rise speed is 5 ℃/min;
fig. 1(b) is a TEM image of the graphene/Ni composite material prepared in comparative example 1, and it can be seen that Ni nanoparticles cannot be observed for the stacked graphite sheets, indicating that aggregation and stacking of graphite sheets cannot be prevented without bacteria-mediated electrostatic adsorption.
The electrochemical properties were measured in the same manner as in example 1.
At 20mA cm-2The overpotential at the current density of (1) is 470mV, which is much higher than that of the example (-250 mV), and the Tafel slope is 207mV dec-1Indicating a poor mass/charge transfer process. The results demonstrate Ni/Ni by bio-mediated in situ sulfidation and self-growth3S2The nanoclusters can obviously optimize the structure and the electrocatalytic activity of the composite hybrid.
Comparative example 2
The preparation method of the graphene/CdS composite material related to the comparative example adopts the same steps as the example, but Ni is not related to the condition2+The adsorption comprises the following specific steps:
(1) CdS-bacteria/GO precursors were prepared according to the steps (1), (2), (3) and (4) in example 1.
(2) Carrying out vacuum freeze drying on the obtained CdS/GO precursor to constant weight, and then carrying out pyrolysis reaction in an inert atmosphere to obtain the graphene/CdS composite material, wherein the pyrolysis treatment atmosphere is a nitrogen atmosphere, the temperature is 700 ℃, the carbonization treatment time is 2h, and the temperature rise speed is 5 ℃/min;
the atomic ratio of C/Cd/S in the graphene/CdS composite material prepared in the comparative example 2 was 76.85/11.52/11.63, indicating that no Ni was present2+The pyrolysis of CdS/GO hybrid under the conditions of (1) cannot reduce and remove Cd2+The remaining CdS nanoparticles do not have OER catalytic activity. The results show Ni2+Catalytic reduction of Cd in pyrolysis2+So as to form elemental Cd steam release, and simultaneously Ni reacts with the reserved S source to realize in-situ vulcanization and self-growth to form Ni/Ni3S2The nanoclusters serve as efficient catalytic active centers and are anchored on the graphene.
Comparative example 3
(1) Seed liquid of Pandoraea sp.B-6 was obtained by culturing according to the procedures (1) and (2) of example 1.
(2) Centrifuging the obtained Pandoraea sp.B-6 seed solution for 5 minutes at 8000rpm, discarding supernatant, and collecting thallus;
(3) inoculating the collected Pandoraea sp.B-6 thallus into a Cd-containing sterile culture medium according to the inoculation amount of 10% (the ratio of the volume of the bacterium liquid transferred to the volume of the culture liquid after inoculation), culturing at the temperature of 30 ℃ and natural pH for 18h, and centrifuging at the rotating speed of 8,000rpm for 5min to separate to obtain bacterial thallus; the Cd-containing sterile culture medium comprises the following components in parts by weight: glucose 2g/L, Cd (NO)3)2，0.4mM，NH4Cl1.5 g/L，MgCl2 0.2g/L， CaCl2 0.01g/L，FeSO4·7H2O 0.015g/L，MnSO4·H2O 0.01g/L；MOPs8.314g/L， trineg/L，L-cysteine 0.1mM。
(4) And (3) dispersing the CdS-bacterial precursor obtained in the last step in 200mL of pure water, adjusting the concentration to OD600 to be 2, adding 50mL of GO solution with the concentration of 0.5mg/mL, and magnetically stirring for 30 min. Centrifuging at 8,000rpm for 5min to obtain CdS-bacteria/GO hybrid.
(5) Dispersing the obtained CdS-bacterium/GO hybrid in 100mLNiCl with a concentration of 5g/L2Magnetically stirring the solution for 4h, and centrifuging the solution at 8,000rpm for 5min to obtain the CdS-bacterium/GO/Ni composite precursor.
(6) Carrying out vacuum freeze drying on the obtained CdS-bacterium/GO/Ni composite precursor to constant weight, and carrying out pyrolysis reaction in inert atmosphere to obtain graphene supported Ni/Ni3S2The atmosphere of the pyrolysis treatment is nitrogen atmosphere, the temperature is 900 ℃, the time of carbonization treatment is 2h, and the temperature rise speed is 5 ℃/min;
the electrochemical properties were measured in the same manner as in example 1.
The catalyst material prepared by the present comparative example 3 was scanned at a rate of 5mV/s at 100mA cm-2Has an overpotential of 450mV and a Tafel slope of 76mV dec-1. Pyrolysis temperature has a significant effect on the catalyst structure, and too high a pyrolysis temperature can cause catalytic graphitization of Ni so that a thicker graphite shell is formed, which can hinder accessibility of active sites, thereby affecting catalytic activity. It can be seen that the pyrolysis temperature is on the graphene supported Ni/Ni3S2The formation of the nanocluster composite structure plays a crucial role.
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