WO2018076462A1 - Preparation method for reduced graphene oxide/aspergillus niger cellulose aerogel - Google Patents

Preparation method for reduced graphene oxide/aspergillus niger cellulose aerogel Download PDF

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WO2018076462A1
WO2018076462A1 PCT/CN2016/108703 CN2016108703W WO2018076462A1 WO 2018076462 A1 WO2018076462 A1 WO 2018076462A1 CN 2016108703 W CN2016108703 W CN 2016108703W WO 2018076462 A1 WO2018076462 A1 WO 2018076462A1
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graphene oxide
aspergillus niger
cellulose aerogel
aerogel
aspergillus
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PCT/CN2016/108703
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French (fr)
Chinese (zh)
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赖跃坤
李淑芬
张理源
王涛
陈国强
何志成
黄剑莹
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苏州蓝锐纳米科技有限公司
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    • 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
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
    • 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
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels

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  • the invention relates to the technical field of microbial fermentation and aerogel materials, in particular to a method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel.
  • An aerogel material generally refers to a lightweight porous solid phase material having a three-dimensional network skeleton structure composed of nanoparticles and a gas phase medium filled with a porosity of more than 90%.
  • aerogel has a low refractive index due to the three-dimensional network skeleton structure, low node constant ( ⁇ 1.01), low density (only 2-3 times of air, can be reduced to 3mg) /cm 3 ), high optical transmittance (93%) and low thermal conductivity [ ⁇ 0.01W/(m ⁇ k)] are widely used in superabsorbent materials, thermal insulation materials, and impact resistance. Materials and fields of conductive energy storage materials. At present, there are many researches on synthetic polymer aerogels.
  • Synthetic polymer aerogels have high strength and high elasticity.
  • synthetic polymers are not as widely sourced as natural polymers, low in cost, and less polluting to the environment. With the depletion of resources, the development of new renewable, sustainable and environmentally friendly materials has become a top priority.
  • Graphene oxide aerogel like other inorganic material aerogels, has the biggest disadvantages of poor mechanical properties and high brittleness, which greatly limits its application in many fields.
  • the preparation of cellulose aerogel or inorganic material aerogel alone will have many shortcomings, such as poor mechanical properties, poor elasticity, and poor adsorption properties.
  • the graphene oxide aerogel disclosed in U.S. Patent No. 8,881,821 B2 has the above problems.
  • the research direction is multi-component doping, which will inevitably impart aerogel functionality and improve its mechanical properties, so that the cellulose aerogel has good mechanical properties, flexibility and energy. It is used in areas such as environmental pollution, energy conservation and emission reduction.
  • Chinese patent CN201610011889.2 discloses a graphene/hyphae hydrogel loaded with nanoparticles and a preparation method and application thereof.
  • the nanoparticles are dispersed in the graphene, and the filamentous fungal hyphae matrix is added for mixing, and under hydrothermal reaction conditions, they are cross-linked to form a ternary conforming hydrogel.
  • This structure due to mycelial formation The structure has been made and then the graphene and nanoparticles are attached to the already formed hyphae frame by physical means.
  • the overall hyphae structure is not harmonious and stable, which is equivalent to graphene and nanoparticles being foreign media, which is imposed on the mycelium framework, and the hyphae frame itself cannot be deformed by itself, and can only be adaptively deformed under the action of external force. It is bound to affect the stability of the mycelial framework.
  • the technical problem solved by the invention is to provide a preparation method of reduced graphene oxide/Aspergillus niger cellulose aerogel with good hyphal structure stability.
  • a method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel comprises the following steps:
  • the bacteria ball cultured in the step (1) is washed with deionized water and freeze-dried by a freeze-drying technique to form a graphene oxide/Aspergillus niger cellulose aerogel;
  • the graphene oxide/A. niger cellulose aerogel prepared in the step (2) is subjected to carbonization treatment to obtain a hydrophobic graphene oxide/Aspergillus niger cellulose aerogel having hydrophobicity.
  • This application is a combination of Aspergillus niger and graphene oxide during the breeding process. Therefore, the combination of Aspergillus niger cellulose and graphene oxide is naturally stable, and the mycelium structure is more stable than the existing pure mechanical mixing. At the same time, through the carbonization treatment, the aerogel can obtain excellent properties such as good hydrophobic properties and lipophilic properties, and can be used as an adsorbent material.
  • the concentration of the graphene oxide dispersion in the step (1) is 0.5-8 mg/mL, and the volume ratio of the graphene oxide dispersion to the medium solution is 1:200 to 1:20, and the step ( 1)
  • the medium culture conditions are: temperature 30-37 ° C, and the culture time is 36-72 h.
  • the lyophilization technique in the step (2) is freeze drying, liquid nitrogen freeze drying or supercritical carbon dioxide drying.
  • the carbonization temperature in the step (3) is 700-1000 ° C for 2 h.
  • the invention has the beneficial effects that the hyphae structure is stable, has good hydrophobicity and lipophilicity, and can be used as an adsorbing material.
  • the adsorption rate can reach more than 30 times.
  • Figure 1 is an SEM image of the aerogel prepared in Example 1.
  • Figure 2 is an SEM image of the aerogel prepared in Example 2.
  • Figure 3 is an SEM image of the aerogel prepared in Example 3.
  • Figure 4 is an SEM image of the aerogel prepared in Example 4.
  • Figure 5 is an SEM image of the Aspergillus niger cellulose aerogel in Example 5.
  • Figure 6 shows the infrared spectrum of the aerogel in the case of different volume ratios.
  • Figure 7 shows the XPS spectra of aerogels at different volume ratios.
  • Fig. 8 is a schematic view showing the contact angle of the reduced graphene oxide/A. niger cellulose aerogel in the case where the content of the reduced graphene oxide is different.
  • Figure 9 is an optical photograph of the reduced graphene oxide/Aspergillus niger aerogel adsorbed surface light oil (hexadecane as a target oil agent) prepared in Example 4.
  • Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ⁇ 7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage.
  • the obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, carbonization treatment, the graphene oxide / Aspergillus cellulose aerogel is placed in a tube furnace and calcined at 700 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample, the gas The gel has a certain hydrophobic effect and can be used to adsorb pollutants such as oil and purify the water.
  • Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ⁇ 7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage.
  • the obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel.
  • the graphene oxide/Aspergillus cellulose aerogel was placed in a tube furnace and calcined at 800 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample, the aerogel has A certain hydrophobic effect can be used to adsorb pollutants such as oil and purify water.
  • the surface morphology of the reduced graphene oxide/A. niger cellulose aerogel prepared in Example 2 was characterized as shown in FIG.
  • Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ⁇ 7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage.
  • the obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, the graphene oxide/A. niger cellulose aerogel was placed in a tube furnace and calcined at 900 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample.
  • a certain hydrophobic effect can be used to adsorb pollutants such as oil and purify water.
  • the surface morphology of the reduced graphene oxide/Aspergillus niger cellulose aerogel prepared in Example 2 was characterized as shown in FIG.
  • Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ⁇ 7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage.
  • the obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, the graphene oxide/A. niger cellulose aerogel was placed in a tube furnace and calcined at 900 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample.
  • a certain hydrophobic effect can be used to adsorb pollutants such as oil and purify water.
  • the surface morphology of the reduced graphene oxide/Aspergillus niger cellulose aerogel prepared in Example 2 was characterized as shown in FIG.
  • This example is a comparative example to prepare a Aspergillus niger cellulose aerogel.
  • the specific preparation process is: inoculation of several Aspergillus niger spores in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ⁇ 7H 2 O, In a conical flask of 1 g/L KH 2 PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench.
  • potato-containing medium medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ⁇ 7H 2 O
  • the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench.
  • the Aspergillus niger was extensively propagated, it was taken out from the culture flask and thoroughly washed with deionized water several times, placed in a round petri dish and frozen in a -80 ° C refrigerator and then placed in a lyophilizer. After lyophilization for 48 h, the Aspergillus niger cellulose aerogel was finally obtained.
  • the surface morphology of the prepared Aspergillus niger cellulose aerogel was characterized in this comparative example. As shown in Fig. 5, the Aspergillus niger cellulose aerogel exhibited a porous network structure with a fiber diameter of 5-10 ⁇ m.
  • Figure 6 is an infrared spectrum of a reduced aerobic graphene oxide/A. niger cellulose aerogel and a different volume ratio, wherein 1:100 means the volume of the graphene oxide dispersion and the potato The volume ratio of the medium solution. Other ratios can be deduced by analogy. It can be seen that the infrared spectrum of the Aspergillus niger aerogel has many peaks corresponding to the absorption positions of some or some functional groups.
  • the peak appearing at one point is attributed to the stretching of the protein macromolecular amide bond; in addition, the peak around 1100 cm -1 is mainly caused by the polysaccharide.
  • the peak position corresponding to the functional group contained in the aerogel does not change, but the peak intensity increases.
  • the acid group contained partially or even completely reduced graphene oxide.
  • Figure 7 shows the XPS spectra of the reduced graphene oxide/A. niger cellulose aerogel and the different volume ratios of Aspergillus niger cellulose aerogel. Wherein 1:100 means the volume ratio of the graphene oxide dispersion volume to the potato medium solution. Other ratios can be deduced by analogy. It can be seen from the spectral results that both the Aspergillus niger cellulose aerogel and the reduced graphene oxide/A. niger co-culture aerogel are mainly composed of C and O elements.
  • Figure 8 is a picture of the contact angle of the reduced graphene oxide/Aspergillus cellulose aerogel. It can be seen from the results that as the content of reduced graphene oxide increases, the contact angle of the reduced graphene oxide/Aspergillus niger cellulose aerogel is larger, and the hydrophobic property is better.
  • Figure 9 is an optical photograph of the reduced graphene oxide/Aspergillus niger aerogel adsorbed surface light oil (hexadecane as a target oil agent) prepared in Example 4.
  • the carbonized graphene oxide/Aspergillus cellulose aerogel has hydrophobicity and lipophilic properties and is used as a good adsorbent material.
  • hexadecane was used as the target contaminant and stained with oil red O.
  • the dyed cetane solution was quickly taken by it. Absorbed, leaving a clear water surface.
  • the hexadecane was calculated to be 34.74 times.

Abstract

Provided is a preparation method for a reduced graphene oxide/Aspergillus niger cellulose aerogel, comprising (1), mixing a graphene oxide dispersion, Aspergillus niger and a culture medium solution, and co-culturing same under conditions suitable for Aspergillus niger reproduction so as to form a ball of Aspergillus niger coated with the graphene oxide dispersion; (2), washing the ball cultured in step (1) with deionized water until clean and freeze-drying and shaping same by utilizing a freeze-drying technology so as to form a graphene oxide/Aspergillus niger cellulose aerogel; and (3), subjecting the graphene oxide/Aspergillus niger cellulose aerogel prepared in step (2) to carbonization treatment so as to obtain the reduced graphene oxide/Aspergillus niger cellulose aerogel having hydrophobicity. The hypha obtained by the method has a stable structure, has a good hydrophobicity and lipophilicity, and can be used as an adsorbing material.

Description

一种还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法Preparation method of reduced graphene oxide/Aspergillus niger cellulose aerogel 技术领域Technical field
本发明涉及微生物发酵及气凝胶材料技术领域，尤其涉及一种还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法。The invention relates to the technical field of microbial fermentation and aerogel materials, in particular to a method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel.
背景技术Background technique
气凝胶材料一般是指具有高达90％以上孔隙率，由纳米颗粒构成、气相介质填充的三维立体网络骨架结构的轻质多孔固相材料。气凝胶作为一种轻质多孔固相材料，由于三维网络骨架结构而具有较低的折射系数，低节点常数(<1.01)、低密度(仅为空气的2-3倍，可降至3mg/cm3)、高的光学透过率(93％)以及低的导热率[～0.01W/(m·k)]的性质，被广泛用于超强吸附材料、保温隔热材料、防冲击材料以及导电储能材料领域。目前合成高分子气凝胶的研究已经有很多，合成高分子气凝胶具有高强力、高弹性，然而，合成高分子不像天然高分子来源广泛，成本低廉，对环境污染小，随着石油资源的日益枯竭，开发新型可再生、可持续、绿色环保型材料成为重中之重。An aerogel material generally refers to a lightweight porous solid phase material having a three-dimensional network skeleton structure composed of nanoparticles and a gas phase medium filled with a porosity of more than 90%. As a lightweight porous solid phase material, aerogel has a low refractive index due to the three-dimensional network skeleton structure, low node constant (<1.01), low density (only 2-3 times of air, can be reduced to 3mg) /cm 3 ), high optical transmittance (93%) and low thermal conductivity [~0.01W/(m·k)] are widely used in superabsorbent materials, thermal insulation materials, and impact resistance. Materials and fields of conductive energy storage materials. At present, there are many researches on synthetic polymer aerogels. Synthetic polymer aerogels have high strength and high elasticity. However, synthetic polymers are not as widely sourced as natural polymers, low in cost, and less polluting to the environment. With the depletion of resources, the development of new renewable, sustainable and environmentally friendly materials has become a top priority.
纤维素气凝胶作为新生的第三代材料，超越传统的硅气凝胶和聚合物基气凝胶，在制备时融入了新的性能，如良好的生物相容性和可降解性，属于生物类聚合物材料，可应用于在制药业、化妆品行业。氧化石墨烯作为重要的石墨烯衍生物之一，是天然石墨经化学剥离得到的一种单层碳原子二维纳米材料。氧化石墨烯通常情况下会表现出两亲性，因其包含丰富的含氧集团，如：-OH，-COOH，C-O-C，—C＝O等，GO在大多数极性溶剂中具备良好的分散性和表面活性，氧化石墨烯独特的结构特征赋予其多种表面特性，使得该材料被广泛应用于构建多孔三维结构。曲霉菌繁殖形成的纤维素真菌是来源丰富的生物质资源，具有可再生、易降解、环保无污染等特点，目前被视为最理想的模板材料。As a new generation of third-generation materials, cellulose aerogels surpass traditional silicone aerogels and polymer-based aerogels, incorporating new properties such as good biocompatibility and degradability. Biopolymer materials can be used in the pharmaceutical and cosmetic industries. Graphene oxide, as one of the important graphene derivatives, is a single-layer carbon atom two-dimensional nanomaterial obtained by chemical stripping of natural graphite. Graphene oxide usually exhibits amphiphilicity because it contains abundant oxygen-containing groups such as -OH, -COOH, COC, -C=O, etc. GO has good dispersion in most polar solvents. Sex and surface activity, the unique structural characteristics of graphene oxide give it a variety of surface characteristics, making this material widely used to construct porous three-dimensional structures. The cellulose fungus formed by the propagation of Aspergillus is a rich source of biomass resources, and has the characteristics of being recyclable, easily degradable, environmentally friendly and non-polluting, and is currently regarded as the most ideal template material.
氧化石墨烯气凝胶跟其他无机材料气凝胶一样，最大的不足是机械性能差、脆性大，这极大限制了它在很多领域的应用。单纯制备纤维素气凝胶或者无机材料气凝胶都会出现很多不足，如机械性能差、弹性差、吸附性能差等。比如美国专利US8871821B2公开的氧化石墨烯气凝胶就存在上述问题。Graphene oxide aerogel, like other inorganic material aerogels, has the biggest disadvantages of poor mechanical properties and high brittleness, which greatly limits its application in many fields. The preparation of cellulose aerogel or inorganic material aerogel alone will have many shortcomings, such as poor mechanical properties, poor elasticity, and poor adsorption properties. For example, the graphene oxide aerogel disclosed in U.S. Patent No. 8,881,821 B2 has the above problems.
为了解决上述问题，目前，研究方向是多组分掺杂，这样势必会赋予气凝胶功能性，提高其机械性能，使得该类纤维素气凝胶具有较好的机械性能、柔弹性并能运用于环境污染、节能减排等领域。但目前，还没有很好的制备方法来实现上述目的。In order to solve the above problems, at present, the research direction is multi-component doping, which will inevitably impart aerogel functionality and improve its mechanical properties, so that the cellulose aerogel has good mechanical properties, flexibility and energy. It is used in areas such as environmental pollution, energy conservation and emission reduction. However, at present, there is no good preparation method to achieve the above purpose.
中国专利CN201610011889.2公开了一种负载纳米粒子的石墨烯/菌丝水凝胶及其制备方法和应用。该方法中，是将纳米粒子、分散在石墨烯中，加入丝状真菌菌丝基体进行混合，在水热反应条件下，使它们发生交联作用，形成三元符合水凝胶。这种结构，由于菌丝形成 的结构已经制成，然后通过物理手段，将石墨烯和纳米粒子附着在已经形成的菌丝构架上。所以其整体菌丝构架不够和谐和稳定，相当于石墨烯和纳米粒子是外来介质，其强加于菌丝构架上，而菌丝构架本身已经无法自主变形，只能在外力作用下进行适应性变形，势必会影响菌丝构架的稳定性。Chinese patent CN201610011889.2 discloses a graphene/hyphae hydrogel loaded with nanoparticles and a preparation method and application thereof. In the method, the nanoparticles are dispersed in the graphene, and the filamentous fungal hyphae matrix is added for mixing, and under hydrothermal reaction conditions, they are cross-linked to form a ternary conforming hydrogel. This structure, due to mycelial formation The structure has been made and then the graphene and nanoparticles are attached to the already formed hyphae frame by physical means. Therefore, the overall hyphae structure is not harmonious and stable, which is equivalent to graphene and nanoparticles being foreign media, which is imposed on the mycelium framework, and the hyphae frame itself cannot be deformed by itself, and can only be adaptively deformed under the action of external force. It is bound to affect the stability of the mycelial framework.
发明内容Summary of the invention
本发明解决的技术问题是提供一种菌丝架构稳定性好的还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法。The technical problem solved by the invention is to provide a preparation method of reduced graphene oxide/Aspergillus niger cellulose aerogel with good hyphal structure stability.
本发明解决其技术问题所采用的技术方案是：The technical solution adopted by the present invention to solve the technical problem thereof is:
一种还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法，包括以下步骤：A method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel comprises the following steps:
(1)将氧化石墨烯分散液、黑曲霉菌以及培养基溶液混合，在黑曲霉菌适宜繁殖的条件下进行共同培养，形成黑曲霉菌包裹氧化石墨烯分散液的菌球；(1) mixing the graphene oxide dispersion, the Aspergillus niger, and the medium solution, and co-cultivating under the condition that the Aspergillus niger is suitable for propagation, forming a microsphere of the Aspergillus-coated graphene oxide dispersion;
(2)将步骤(1)培养的菌球用去离子水清洗干净并利用冻干技术冻干成型，形成氧化石墨烯/黑曲霉菌纤维素气凝胶；(2) The bacteria ball cultured in the step (1) is washed with deionized water and freeze-dried by a freeze-drying technique to form a graphene oxide/Aspergillus niger cellulose aerogel;
(3)将步骤(2)制成的氧化石墨烯/黑曲霉菌纤维素气凝胶进行碳化处理得到具有疏水性的还原氧化石墨烯/黑曲霉菌纤维素气凝胶。(3) The graphene oxide/A. niger cellulose aerogel prepared in the step (2) is subjected to carbonization treatment to obtain a hydrophobic graphene oxide/Aspergillus niger cellulose aerogel having hydrophobicity.
本申请是黑曲霉菌在繁殖过程中与氧化石墨烯进行结合，因此，黑曲霉菌纤维素与氧化石墨烯的结合自然稳定，相比现有的纯机械式混合，其菌丝架构更加稳定。同时，通过碳化处理，可以使得气凝胶获得良好的疏水性能和亲油性能等优良性能，可以作为吸附材料使用。This application is a combination of Aspergillus niger and graphene oxide during the breeding process. Therefore, the combination of Aspergillus niger cellulose and graphene oxide is naturally stable, and the mycelium structure is more stable than the existing pure mechanical mixing. At the same time, through the carbonization treatment, the aerogel can obtain excellent properties such as good hydrophobic properties and lipophilic properties, and can be used as an adsorbent material.
进一步的是：所述步骤(1)中氧化石墨烯分散液的浓度为0.5-8mg/mL，氧化石墨烯分散液与培养基溶液的体积比为1:200～1:20，所述步骤(1)中培养条件为：温度30-37℃，培养时间为36-72h。Further, the concentration of the graphene oxide dispersion in the step (1) is 0.5-8 mg/mL, and the volume ratio of the graphene oxide dispersion to the medium solution is 1:200 to 1:20, and the step ( 1) The medium culture conditions are: temperature 30-37 ° C, and the culture time is 36-72 h.
进一步的是：所述步骤(2)中冻干技术为冷冻干燥、液氮冷冻干燥或超临界二氧化碳干燥。Further, the lyophilization technique in the step (2) is freeze drying, liquid nitrogen freeze drying or supercritical carbon dioxide drying.
进一步的是：所述步骤(3)中碳化温度为700-1000℃，时间2h。Further, the carbonization temperature in the step (3) is 700-1000 ° C for 2 h.
本发明的有益效果是：菌丝架构稳定，具有良好的疏水性和亲油性，可用于作为吸附材料使用。吸附率可达30倍以上。The invention has the beneficial effects that the hyphae structure is stable, has good hydrophobicity and lipophilicity, and can be used as an adsorbing material. The adsorption rate can reach more than 30 times.
附图说明DRAWINGS
图一为实施例1所制备的气凝胶的SEM图。Figure 1 is an SEM image of the aerogel prepared in Example 1.
图二为实施例2所制备的气凝胶的SEM图。Figure 2 is an SEM image of the aerogel prepared in Example 2.
图三为实施例3所制备的气凝胶的SEM图。Figure 3 is an SEM image of the aerogel prepared in Example 3.
图四为实施例4所制备的气凝胶的SEM图。 Figure 4 is an SEM image of the aerogel prepared in Example 4.
图五为实施例5中黑曲霉菌纤维素气凝胶的SEM图。Figure 5 is an SEM image of the Aspergillus niger cellulose aerogel in Example 5.
图六为不同体积比的情况下气凝胶的红外谱图。Figure 6 shows the infrared spectrum of the aerogel in the case of different volume ratios.
图七为不同体积比的情况下气凝胶的XPS谱图。Figure 7 shows the XPS spectra of aerogels at different volume ratios.
图八为还原氧化石墨烯含量不同的情况下，还原氧化石墨烯/黑曲霉菌纤维素气凝胶接触角示意图。Fig. 8 is a schematic view showing the contact angle of the reduced graphene oxide/A. niger cellulose aerogel in the case where the content of the reduced graphene oxide is different.
图九为实施例4所制备的还原氧化石墨烯/黑曲霉菌气凝胶吸附水面轻油(十六烷作为目标油剂)的光学照片。Figure 9 is an optical photograph of the reduced graphene oxide/Aspergillus niger aerogel adsorbed surface light oil (hexadecane as a target oil agent) prepared in Example 4.
具体实施方式detailed description
下面结合附图和具体实施方式对本发明进一步说明。The invention is further described below in conjunction with the drawings and specific embodiments.
实施例1：Example 1:
将黑曲霉菌孢若干个接种在100mL装有土豆培养基(培养基成分：200g/L土豆，20g/L C6H12O6、0.5g/L MgSO4·7H2O、1g/L KH2PO4)的锥形瓶中，37℃下摇床培养48h，整个操作需在超净工作台里进行。待黑曲霉菌大量繁殖后，将其转移到4℃冰箱储存。随后将100mL土豆培养基和1mg/L氧化石墨烯分散液121℃高温灭菌20min，灭菌结束后，将培养基和氧化石墨烯分散液取出冷却至室温并分别取氧化石墨烯分散液3mL、黑曲霉菌菌种溶液10mL加入到培养基中，37℃下摇床培养72h，培养得到黑曲霉菌包裹氧化石墨烯的氧化石墨烯/黑曲霉菌菌球。将得到的菌球用去离子水清洗若干遍后，将其放置在圆形培养皿中并液氮直接冻实随后在冻干机中冻干48h，获得氧化石墨烯/黑曲霉菌纤维素气凝胶。最后碳化处理，将氧化石墨烯/黑曲霉菌纤维素气凝胶放置在管式炉并在惰性气体氩气保护下700℃煅烧2h得到还原氧化石墨烯/黑曲霉菌气凝胶样品，该气凝胶具有一定的疏水效果，可用于吸附油剂等污染物，净化水体。Several Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ·7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage. Subsequently, 100 mL of potato medium and 1 mg/L of graphene oxide dispersion were autoclaved at 121 ° C for 20 min. After sterilization, the medium and the graphene oxide dispersion were taken out and cooled to room temperature, and 3 mL of a graphene oxide dispersion was respectively taken. 10 mL of the Aspergillus sp. solution was added to the medium, and shaken at 37 ° C for 72 h to obtain a graphene oxide/Aspergillus sp. ball of Aspergillus-coated graphene oxide. The obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, carbonization treatment, the graphene oxide / Aspergillus cellulose aerogel is placed in a tube furnace and calcined at 700 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample, the gas The gel has a certain hydrophobic effect and can be used to adsorb pollutants such as oil and purify the water.
对实施例1所制备的还原氧化石墨烯/黑曲霉菌纤维素气凝胶进行表面形貌表征，如图一所示，还原氧化石墨烯片层与黑曲霉菌菌丝相互交联并形成孔洞，这有利于增大孔隙率，降低气凝胶的密度。The surface morphology of the reduced graphene oxide/A. niger cellulose aerogel prepared in Example 1 was characterized. As shown in FIG. 1, the reduced graphene oxide sheet and the Aspergillus niger hyphae were cross-linked and formed a hole. This is beneficial to increase the porosity and reduce the density of the aerogel.
实施例2：Example 2:
将黑曲霉菌孢若干个接种在100mL装有土豆培养基(培养基成分：200g/L土豆，20g/L C6H12O6、0.5g/L MgSO4·7H2O、1g/L KH2PO4)的锥形瓶中，37℃下摇床培养48h，整个操作需在超净工作台里进行。待黑曲霉菌大量繁殖后，将其转移到4℃冰箱储存。随后将100mL土豆培养基和1mg/L氧化石墨烯分散液121℃高温灭菌20min，灭菌结束后，将培养基和氧化石墨烯分散液取出冷却至室温并分别取氧化石墨烯分散液5mL、黑曲霉菌菌种溶液10mL 加入到培养基中，37℃下摇床培养72h，培养得到黑曲霉菌包裹氧化石墨烯的氧化石墨烯/黑曲霉菌菌球。将得到的菌球用去离子水清洗若干遍后，将其放置在圆形培养皿中并液氮直接冻实随后在冻干机中冻干48h，获得氧化石墨烯/黑曲霉菌纤维素气凝胶。最后将氧化石墨烯/黑曲霉菌纤维素气凝胶放置在管式炉并在惰性气体氩气保护下800℃煅烧2h得到还原氧化石墨烯/黑曲霉菌气凝胶样品，该气凝胶具有一定的疏水效果，可用于吸附油剂等污染物，净化水体。Several Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ·7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage. Subsequently, 100 mL of potato medium and 1 mg/L of graphene oxide dispersion were autoclaved at 121 ° C for 20 min. After the sterilization was completed, the medium and the graphene oxide dispersion were taken out and cooled to room temperature, and respectively, 5 mL of the graphene oxide dispersion was taken. 10 mL of the Aspergillus strain solution was added to the medium, and cultured at 37 ° C for 72 hours on a shaker to obtain a graphene oxide/Aspergillus niger ball coated with Aspergillus niger. The obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, the graphene oxide/Aspergillus cellulose aerogel was placed in a tube furnace and calcined at 800 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample, the aerogel has A certain hydrophobic effect can be used to adsorb pollutants such as oil and purify water.
对实施例2所制备的还原氧化石墨烯/黑曲霉菌纤维素气凝胶进行表面形貌表征，如图二所示。The surface morphology of the reduced graphene oxide/A. niger cellulose aerogel prepared in Example 2 was characterized as shown in FIG.
实施例3：Example 3:
将黑曲霉菌孢若干个接种在100mL装有土豆培养基(培养基成分：200g/L土豆，20g/L C6H12O6、0.5g/L MgSO4·7H2O、1g/L KH2PO4)的锥形瓶中，37℃下摇床培养48h，整个操作需在超净工作台里进行。待黑曲霉菌大量繁殖后，将其转移到4℃冰箱储存。随后将100mL土豆培养基和1mg/L氧化石墨烯分散液121℃高温灭菌20min，灭菌结束后，将培养基和氧化石墨烯分散液取出冷却至室温并分别取氧化石墨烯分散液8mL、黑曲霉菌菌种溶液10mL加入到培养基中，37℃下摇床培养72h，培养得到黑曲霉菌包裹氧化石墨烯的氧化石墨烯/黑曲霉菌菌球。将得到的菌球用去离子水清洗若干遍后，将其放置在圆形培养皿中并液氮直接冻实随后在冻干机中冻干48h，获得氧化石墨烯/黑曲霉菌纤维素气凝胶。最后将氧化石墨烯/黑曲霉菌纤维素气凝胶放置在管式炉并在惰性气体氩气保护下900℃煅烧2h得到还原氧化石墨烯/黑曲霉菌气凝胶样品，该气凝胶具有一定的疏水效果，可用于吸附油剂等污染物，净化水体。Several Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ·7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage. Subsequently, 100 mL of potato medium and 1 mg/L of graphene oxide dispersion were autoclaved at 121 ° C for 20 min. After sterilization, the medium and the graphene oxide dispersion were taken out and cooled to room temperature, and 8 mL of a graphene oxide dispersion was respectively taken. 10 mL of the Aspergillus sp. solution was added to the medium, and shaken at 37 ° C for 72 h to obtain a graphene oxide/Aspergillus sp. ball of Aspergillus-coated graphene oxide. The obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, the graphene oxide/A. niger cellulose aerogel was placed in a tube furnace and calcined at 900 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample. A certain hydrophobic effect can be used to adsorb pollutants such as oil and purify water.
对实施例2所制备的还原氧化石墨烯/黑曲霉菌纤维素气凝胶进行表面形貌表征，如图三所示。The surface morphology of the reduced graphene oxide/Aspergillus niger cellulose aerogel prepared in Example 2 was characterized as shown in FIG.
实施例4：Example 4:
将黑曲霉菌孢若干个接种在100mL装有土豆培养基(培养基成分：200g/L土豆，20g/L C6H12O6、0.5g/L MgSO4·7H2O、1g/L KH2PO4)的锥形瓶中，37℃下摇床培养48h，整个操作需在超净工作台里进行。待黑曲霉菌大量繁殖后，将其转移到4℃冰箱储存。随后将100mL土豆培养基和1mg/L氧化石墨烯分散液121℃高温灭菌20min，灭菌结束后，将培养基和氧化石墨烯分散液取出冷却至室温并分别取氧化石墨烯分散液10mL、黑曲霉菌菌种溶液10mL加入到培养基中，37℃下摇床培养72h，培养得到黑曲霉菌包裹氧化石墨烯的氧化石墨烯/黑 曲霉菌菌球。将得到的菌球用去离子水清洗若干遍后，将其放置在圆形培养皿中并液氮直接冻实随后在冻干机中冻干48h，获得氧化石墨烯/黑曲霉菌纤维素气凝胶。最后将氧化石墨烯/黑曲霉菌纤维素气凝胶放置在管式炉并在惰性气体氩气保护下900℃煅烧2h得到还原氧化石墨烯/黑曲霉菌气凝胶样品，该气凝胶具有一定的疏水效果，可用于吸附油剂等污染物，净化水体。Several Aspergillus niger spores were inoculated in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ·7H 2 O, 1 g/L KH 2 In a conical flask of PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus sp. is extensively propagated, it is transferred to a refrigerator at 4 ° C for storage. Subsequently, 100 mL of potato medium and 1 mg/L of graphene oxide dispersion were autoclaved at 121 ° C for 20 min. After the sterilization was completed, the medium and the graphene oxide dispersion were taken out and cooled to room temperature, and 10 mL of the graphene oxide dispersion was respectively taken. 10 mL of the Aspergillus sp. solution was added to the medium, and shaken at 37 ° C for 72 h to obtain a graphene oxide/Aspergillus sp. ball of Aspergillus-coated graphene oxide. The obtained microspheres were washed several times with deionized water, placed in a circular petri dish and directly frozen in liquid nitrogen, and then lyophilized in a lyophilizer for 48 hours to obtain graphene oxide/Aspergillus niger cellulose gas. gel. Finally, the graphene oxide/A. niger cellulose aerogel was placed in a tube furnace and calcined at 900 ° C for 2 h under inert gas argon gas to obtain a reduced graphene oxide / Aspergillus niger aerogel sample. A certain hydrophobic effect can be used to adsorb pollutants such as oil and purify water.
对实施例2所制备的还原氧化石墨烯/黑曲霉菌纤维素气凝胶进行表面形貌表征，如图四所示。The surface morphology of the reduced graphene oxide/Aspergillus niger cellulose aerogel prepared in Example 2 was characterized as shown in FIG.
实施例5：Example 5:
本实施例是一个对比例子，对比制备黑曲霉菌纤维素气凝胶。具体制备过程为：将黑曲霉菌孢若干个接种在100mL装有土豆培养基(培养基成分：200g/L土豆，20g/L C6H12O6、0.5g/L MgSO4·7H2O、1g/L KH2PO4)的锥形瓶中，37℃下摇床培养48h，整个操作需在超净工作台里进行。待黑曲霉菌大量繁殖后，将其从培养瓶中取出并用去离子水彻底清洗若干遍后，将其放置在圆形培养皿中并在-80℃冰箱中冻实然后放置在冻干机中冻干48h，最终得到黑曲霉菌纤维素气凝胶。本对比例中对所制备的黑曲霉菌纤维素气凝胶的表面形貌进行表征，如图五所示，黑曲霉菌纤维素气凝胶呈现出多孔网络结构，纤维直径在5-10μm。This example is a comparative example to prepare a Aspergillus niger cellulose aerogel. The specific preparation process is: inoculation of several Aspergillus niger spores in 100 mL of potato-containing medium (medium composition: 200 g/L potato, 20 g/L C 6 H 12 O 6 , 0.5 g/L MgSO 4 ·7H 2 O, In a conical flask of 1 g/L KH 2 PO 4 ), the shaker was incubated at 37 ° C for 48 h, and the entire operation was carried out in a clean bench. After the Aspergillus niger was extensively propagated, it was taken out from the culture flask and thoroughly washed with deionized water several times, placed in a round petri dish and frozen in a -80 ° C refrigerator and then placed in a lyophilizer. After lyophilization for 48 h, the Aspergillus niger cellulose aerogel was finally obtained. The surface morphology of the prepared Aspergillus niger cellulose aerogel was characterized in this comparative example. As shown in Fig. 5, the Aspergillus niger cellulose aerogel exhibited a porous network structure with a fiber diameter of 5-10 μm.
图六为黑曲霉菌纤维素气凝胶及不同体积比下，还原氧化石墨烯/黑曲霉菌纤维素气凝胶的红外谱图，其中1：100的含义是氧化石墨烯分散液体积与土豆培养基溶液的体积比。其它比例可以按此类推。可以看出，黑曲霉菌气凝胶红外光谱出现许多峰，分别对应某个或某些官能团的吸收位置。在大约2800cm-1出现的C-H，C-H2及C-H3峰以及1720cm-1处C＝O峰主要是由于脂质与脂肪酸的红外吸收效应；1620cm-1、1540cm-1、1440cm-1以及1380cm-1处出现的峰归因为蛋白质大分子酰胺键伸缩振动；此外，1100cm-1处左右的峰主要是由于多糖引起的。随着纤维素质量分数的增加，气凝胶中包含官能团对应的峰位并没有发生变化，只是峰强有所增加。然而，共培养得到的氧化石墨烯/黑曲霉菌气凝胶除了具备黑曲霉菌气凝胶所特有的官能团外，C＝O双键峰强度发生减弱甚至消失，这说明黑曲霉菌气凝胶所含有的酸性集团部分甚至完全还原了氧化石墨烯。Figure 6 is an infrared spectrum of a reduced aerobic graphene oxide/A. niger cellulose aerogel and a different volume ratio, wherein 1:100 means the volume of the graphene oxide dispersion and the potato The volume ratio of the medium solution. Other ratios can be deduced by analogy. It can be seen that the infrared spectrum of the Aspergillus niger aerogel has many peaks corresponding to the absorption positions of some or some functional groups. CH at about 2800cm -1 appears, CH 2 and CH 3, and the peak at 1720cm -1 C = O peak is mainly due to the infrared absorbing effect of lipid fatty acids; 1620cm -1, 1540cm -1, 1440cm -1 and 1380cm - The peak appearing at one point is attributed to the stretching of the protein macromolecular amide bond; in addition, the peak around 1100 cm -1 is mainly caused by the polysaccharide. As the mass fraction of cellulose increases, the peak position corresponding to the functional group contained in the aerogel does not change, but the peak intensity increases. However, the co-cultured graphene oxide/Aspergillus niger aerogel has a functional group unique to Aspergillus niger aerogel, and the C=O double bond peak intensity is weakened or even disappeared, indicating that the Aspergillus niger aerogel The acid group contained partially or even completely reduced graphene oxide.
图七为黑曲霉菌纤维素气凝胶及不同体积比下，还原氧化石墨烯/黑曲霉菌纤维素气凝胶的XPS谱图。其中1：100的含义是氧化石墨烯分散液体积与土豆培养基溶液的体积比。其它比例可以按此类推。从谱图结果可以看出，不管是黑曲霉菌纤维素气凝胶还是还原氧化石墨烯/黑曲霉菌共培养气凝胶都主要由C、O元素组成。 Figure 7 shows the XPS spectra of the reduced graphene oxide/A. niger cellulose aerogel and the different volume ratios of Aspergillus niger cellulose aerogel. Wherein 1:100 means the volume ratio of the graphene oxide dispersion volume to the potato medium solution. Other ratios can be deduced by analogy. It can be seen from the spectral results that both the Aspergillus niger cellulose aerogel and the reduced graphene oxide/A. niger co-culture aerogel are mainly composed of C and O elements.
图八为还原氧化石墨烯/黑曲霉菌纤维素气凝胶接触角图片。从结果可以看出，随着还原氧化石墨烯含量的增加，还原氧化石墨烯/黑曲霉菌纤维素气凝胶的接触角越大，疏水性能越好。Figure 8 is a picture of the contact angle of the reduced graphene oxide/Aspergillus cellulose aerogel. It can be seen from the results that as the content of reduced graphene oxide increases, the contact angle of the reduced graphene oxide/Aspergillus niger cellulose aerogel is larger, and the hydrophobic property is better.
图九为实施4所制备的还原氧化石墨烯/黑曲霉菌气凝胶吸附水面轻油(十六烷作为目标油剂)的光学照片。碳化后的氧化石墨烯/黑曲霉菌纤维素气凝胶具有疏水性和亲油性能，被用作良好的吸附材料。在本实验中，十六烷作为目标污染物并用油红O染色，当还原氧化石墨烯/黑曲霉菌纤维素气凝胶接触到水面油剂时，被染色的十六烷溶液很快被其吸收，留下澄清的水面。继续向水面滴加十六烷，直至气凝胶吸附达到饱和状态，计算其吸附率为34.74倍。Figure 9 is an optical photograph of the reduced graphene oxide/Aspergillus niger aerogel adsorbed surface light oil (hexadecane as a target oil agent) prepared in Example 4. The carbonized graphene oxide/Aspergillus cellulose aerogel has hydrophobicity and lipophilic properties and is used as a good adsorbent material. In this experiment, hexadecane was used as the target contaminant and stained with oil red O. When the reduced graphene oxide/aspergillus cellulose aerogel was exposed to the surface oil, the dyed cetane solution was quickly taken by it. Absorbed, leaving a clear water surface. Continue to add hexadecane to the surface until the aerogel adsorption reached saturation, and the adsorption rate was calculated to be 34.74 times.
以上所述的具体实施例，对本发明的目的、技术方案和有益效果进行了进一步详细说明，所应理解的是，以上所述仅为本发明的具体实施例而已，并不用于限制本发明，凡在本发明的精神和原则之内，所做的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。 The specific embodiments of the present invention have been described in detail, and are not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and scope of the present invention are intended to be included within the scope of the present invention.

Claims (4)

  1. 一种还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法，其特征在于，包括以下步骤：A method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel, comprising the steps of:
    (1)将氧化石墨烯分散液、黑曲霉菌以及培养基溶液混合，在黑曲霉菌适宜繁殖的条件下进行共同培养，形成黑曲霉菌包裹氧化石墨烯分散液的菌球；(1) mixing the graphene oxide dispersion, the Aspergillus niger, and the medium solution, and co-cultivating under the condition that the Aspergillus niger is suitable for propagation, forming a microsphere of the Aspergillus-coated graphene oxide dispersion;
    (2)将步骤(1)培养的菌球用去离子水清洗干净并利用冻干技术冻干成型，形成氧化石墨烯/黑曲霉菌纤维素气凝胶；(2) The bacteria ball cultured in the step (1) is washed with deionized water and freeze-dried by a freeze-drying technique to form a graphene oxide/Aspergillus niger cellulose aerogel;
    (3)将步骤(2)制成的氧化石墨烯/黑曲霉菌纤维素气凝胶进行碳化处理得到具有疏水性的还原氧化石墨烯/黑曲霉菌纤维素气凝胶。(3) The graphene oxide/A. niger cellulose aerogel prepared in the step (2) is subjected to carbonization treatment to obtain a hydrophobic graphene oxide/Aspergillus niger cellulose aerogel having hydrophobicity.
  2. 如权利要求1所述的还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法，其特征在于，所述步骤(1)中氧化石墨烯分散液的浓度为0.5-8mg/mL，氧化石墨烯分散液与培养基溶液的体积比为1:200～1:20，所述步骤(1)中培养条件为：温度30-37℃，培养时间为36-72h。The method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel according to claim 1, wherein the concentration of the graphene oxide dispersion in the step (1) is 0.5-8 mg/mL, and the oxidation The volume ratio of the graphene dispersion to the medium solution is 1:200 to 1:20, and the culture condition in the step (1) is: temperature 30-37 ° C, and the culture time is 36-72 h.
  3. 如权利要求1所述的还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法，其特征在于，所述步骤(2)中冻干技术为冷冻干燥、液氮冷冻干燥或超临界二氧化碳干燥。The method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel according to claim 1, wherein the lyophilization technique in the step (2) is freeze drying, liquid nitrogen freeze drying or supercritical carbon dioxide. dry.
  4. 如权利要求1所述的还原氧化石墨烯/黑曲霉菌纤维素气凝胶的制备方法，其特征在于，所述步骤(3)中碳化温度为700-1000℃，时间2h。 The method for preparing a reduced graphene oxide/Aspergillus niger cellulose aerogel according to claim 1, wherein the carbonization temperature in the step (3) is 700-1000 ° C for 2 h.
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