CN109433154B - 三维网状石墨烯气凝胶、其制备方法及其应用 - Google Patents

三维网状石墨烯气凝胶、其制备方法及其应用 Download PDF

Info

Publication number
CN109433154B
CN109433154B CN201811423244.5A CN201811423244A CN109433154B CN 109433154 B CN109433154 B CN 109433154B CN 201811423244 A CN201811423244 A CN 201811423244A CN 109433154 B CN109433154 B CN 109433154B
Authority
CN
China
Prior art keywords
graphene aerogel
temperature
transition metal
dimensional
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201811423244.5A
Other languages
English (en)
Other versions
CN109433154A (zh
Inventor
庄媛
石宝友
王雪纯
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Research Center for Eco Environmental Sciences of CAS
Original Assignee
Research Center for Eco Environmental Sciences of CAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Research Center for Eco Environmental Sciences of CAS filed Critical Research Center for Eco Environmental Sciences of CAS
Priority to CN201811423244.5A priority Critical patent/CN109433154B/zh
Publication of CN109433154A publication Critical patent/CN109433154A/zh
Application granted granted Critical
Publication of CN109433154B publication Critical patent/CN109433154B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0222—Compounds of Mn, Re
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
    • B01J20/0229—Compounds of Fe
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0233—Compounds of Cu, Ag, Au
    • B01J20/0237—Compounds of Cu
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0281—Sulfates of compounds other than those provided for in B01J20/045
    • 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
    • B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
    • B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
    • B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
    • 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
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/72—Copper
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/34—Organic compounds containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C02F2101/38—Organic compounds containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Materials Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

一种三维网状石墨烯气凝胶、其制备方法及其应用，该制备方法包括：(1)将聚合物和过渡金属盐溶于水中，得混合溶液；(2)将该溶液密闭加热；(3)将上述产物先与多糖溶液混合后反复冷解冻，再与过渡金属盐溶液混合形成凝胶；(4)将上述产物在保护气氛、金属基底催化下高温煅烧，即可获得三维网状石墨烯气凝胶。本发明获得的三维网状石墨烯气凝胶相比片状石墨烯具有更丰富的孔隙结构和比表面积，具有优异的吸附和催化性能，形状可控、产量高，在环境和能源领域具有广阔的应用前景。

Description

三维网状石墨烯气凝胶、其制备方法及其应用
技术领域
本发明属于环境功能材料研究领域，具体涉及石墨烯气凝胶及其制备方法，尤其是涉及一种三维网状石墨烯气凝胶、其制备方法及其应用。
背景技术
石墨烯是一种由碳原子以sp2杂化形成的六角蜂窝状排列的、具有原子层厚度的碳纳米材料，因具有高比表面积和优异的电学性能在环境和能源领域得到了广泛的应用。化学气相沉积法因能合成高质量石墨烯而得到了广泛关注。但是，传统化学气相沉积法研究大多利用气相碳源，对于固相碳源关注较少，也尚未见有报道利用络合了金属元素的有机碳源来制备石墨烯。
发明内容
有鉴于此，本发明的主要目的是提供一种全新的三维网状石墨烯气凝胶、其制备方法及其应用。
为了实现上述目的，作为本发明的一个方面，提供了一种三维网状石墨烯气凝胶的制备方法，包括如下步骤：
(1)将聚合物和过渡金属盐溶于水中，得到混合溶液；
(2)将步骤(1)得到的所述混合溶液密闭加热；
(3)将步骤(2)得到的产物先与多糖溶液混合后反复冷解冻，再与过渡金属盐溶液混合形成凝胶；
(4)将步骤(3)得到的凝胶在保护气氛、金属基底催化下高温煅烧，即得到所述三维网状石墨烯气凝胶。
作为本发明的另一个方面，还提供了一种通过如上所述的制备方法制备得到的三维网状石墨烯气凝胶。
作为本发明的再一个方面，还提供了一种如上所述的三维网状石墨烯气凝胶在环境和能源领域中的应用。
基于上述技术方案可知，本发明的三维网状石墨烯气凝胶及其制备方法相对于现有技术至少具有如下有益效果之一：
(1)本发明的三维网状石墨烯气凝胶的制备方法中，利用两种有机质形成双网络凝胶实现了结构的稳定支撑，利用两种有机质与金属的络合键合实现了石墨烯与金属组分的共价键合，获得了具有三维网状结构的石墨烯气凝胶；
(2)本发明的三维网状石墨烯气凝胶相比片状石墨烯具有更丰富的孔隙结构和比表面积，具有优异的吸附和催化性能，形状可控、产量高，在环境和能源领域具有广阔的应用前景。
附图说明
图1为本发明实施例1制备的三维网状石墨烯气凝胶的透射电镜图；
图2为作为实施例1对照的、以单一海藻酸盐凝胶模板制备的石墨烯气凝胶的透射电镜图。
具体实施方式
为使本发明的目的、技术方案和优点更加清楚明白，以下结合具体实施例，并参照附图，对本发明作进一步的详细说明。
本发明不同于传统研究中以单一的非金属有机组分作为碳源，首次采用络合了金属元素的有机双网络凝胶作为碳源，一方面，双网络凝胶作为碳源比普通单一的有机组分具有更好的结构支撑性，使得产物具有更高的比表面积；另一方面，以多糖的羧基络合固定金属离子，以聚乙烯醇的羟基在水热中诱导金属氧化物的有序生长，使得金属组分牢固有序的结合在双网络凝胶上，因而实现了石墨烯与金属组分的共价键合。经对比发现，不同于传统碳源获得的多层片状石墨烯，本发明获得的石墨烯具有网状结构，孔隙更加丰富，具有更加优异的吸附性能，由于石墨烯与金属组分的键合有利于电子传输，也使得材料具有更加优异的催化性能，在环境和能源领域具有广阔的应用前景。
具体地，本发明公开了一种三维网状石墨烯气凝胶的制备方法，包括以下步骤：
(1)将聚合物和过渡金属盐溶于水中，得到混合溶液；
(2)将步骤(1)得到的所述溶液密闭加热；
(3)将步骤(2)得到的产物先与多糖溶液混合后反复冷解冻，再与过渡金属盐溶液混合形成凝胶；
(4)将步骤(3)得到的凝胶产物在保护气氛、金属基底催化下高温煅烧，即得到所述三维网状石墨烯气凝胶。
其中，步骤(1)中的聚合物可以为聚乙烯醇、聚乙二醇等所有脂肪族醇类以及明胶和丝素蛋白等蛋白质以及琼脂等糖类。
其中，步骤(1)中的过渡金属盐例如为铁、钴、铜、银、锰、镍等所有过渡金属的盐类。
其中，步骤(1)中的聚合物浓度为0.01～1000mg/mL，优选为1～10mg/mL，进一步优选10mg/mL；过渡金属盐浓度为0.001～100mol/L，优选为0.1～1mol/L，进一步优选为0.1mol/L。
其中，步骤(2)中的加热温度例如为50℃～400℃，优选为100～120℃，进一步优选为120℃；加热时间例如为6～48h，优选为10～20h，进一步优选为12h。
其中，步骤(2)中的密闭加热例如在聚四氟乙烯反应釜中进行。
其中，步骤(3)中的多糖溶液例如为海藻酸钠、羧甲基纤维素钠或甲壳素的水溶液。
其中，步骤(3)中的冷冻温度例如为-80℃～0℃，优选为-80℃～-40℃，进一步优选为-40℃；解冻通常在室温进行，或者适当升温使整个组分完全解冻；冷解冻的循环次数例如为至少1次，优选为3或4次。
其中，步骤(4)中的保护气氛例如可以采用氮气、氩气等惰性气体或氢气等还原气体来实现。
其中，步骤(4)中的金属基底催化步骤可以采用铁、钴、铜、银、锰、镍等过渡金属基底，其中优选镍基底。
其中，步骤(4)中的高温煅烧温度例如为400～2000℃，优选为600～1000℃，进一步优选为800℃。
其中，步骤(4)中的高温煅烧时间例如为1～24h，优选为1～8h，进一步优选为2h。
本发明还公开了一种通过如上制备方法制备得到的三维网状石墨烯气凝胶。该三维网状石墨烯气凝胶具有高比表面积，例如达到600～1000m2/g，该三维网状石墨烯气凝胶具有优异的吸附性能，例如，对水中100mg/L的四环素吸附去除率大于等于90％；此外，该三维网状石墨烯气凝胶具有优异的催化性能，例如，对水中100mg/mL的环丙沙星通过非均相芬顿催化的去除率大于等于95％。
本发明还公开了一种如上所述的三维网状石墨烯气凝胶在环境和能源领域中的应用。
下面通过具体实施例来对本发明的技术方案作进一步阐述说明。在下述实施例中，使用的实验方法如无特殊说明，均为常规方法。在下述实施例中，所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
本实施例中三维网状石墨烯气凝胶采用以下具体步骤制备而成：
配制聚乙烯醇和亚硫酸铁混合溶液，其中聚乙烯醇在最终溶液中的浓度为10mg/mL、亚硫酸铁在最终溶液中的浓度为0.1mol/L，搅拌形成均匀溶液。将混合溶液放入聚四氟乙烯内衬不锈钢反应釜中在120℃下加热12h，反应结束后向产物溶液中溶解海藻酸钠，海藻酸钠浓度为40mg/mL，搅拌形成均匀溶液，将该溶液逐滴滴入100mL 30mg/mL的亚硫酸铁溶液中，使海藻酸钠与铁离子交联形成凝胶球，将凝胶球在-40℃冷冻12h，再放在室温下解冻12h，反复冷解冻3次使得聚乙烯醇形成凝胶。将该双网络凝胶进行冷冻干燥形成气凝胶，将该气凝胶在N2气氛中保护、镍基底催化下800℃煅烧2h，获得三维网状石墨烯气凝胶，其透射电镜图如图1所示，可见其具有网状结构。为进行对比，将海藻酸铁凝胶在相同条件下煅烧获得三维石墨烯气凝胶，其透射电镜图如图2所示，可见其为多层片状结构。该材料对水中100mg/L的四环素吸附去除率为98.5％，平衡时间为8h；该材料对水中100mg/L的四环素吸附去除率为100％，平衡时间为1h。
实施例2
配制聚乙烯醇和硝酸铜混合溶液，其中聚乙烯醇在最终溶液中的浓度为10mg/mL、硝酸铜在最终溶液中的浓度为0.1mol/L，搅拌形成均匀溶液。将混合溶液放入聚四氟乙烯内衬不锈钢反应釜中在200℃下加热24h，反应结束后向产物溶液中溶解羧甲基纤维素钠，羧甲基纤维素钠的浓度为80mg/mL，搅拌形成均匀溶液，将该溶液逐滴滴入100mL 30mg/mL的硝酸铜溶液中，使羧甲基纤维素钠与铜离子交联形成凝胶球，将该凝胶球在-40℃冷冻12h，再放在室温下解冻12h，反复冷解冻3次使得聚乙烯醇形成凝胶。将该双网络凝胶进行冷冻干燥形成气凝胶，将该气凝胶在N2气氛中保护、镍基底催化下在800℃煅烧1h，获得三维网状石墨烯气凝胶。该凝胶对水中100mg/mL的环丙沙星通过非均相芬顿催化的去除率高达100％。
实施例3
配制明胶和亚硫酸铁混合溶液，其中明胶在最终溶液中的浓度为10mg/mL、亚硫酸铁在最终溶液中的浓度为0.1mol/L，搅拌形成均匀溶液。将混合溶液放入聚四氟乙烯内衬不锈钢反应釜中在150℃下加热12h，反应结束后向产物溶液中溶解海藻酸钠，海藻酸钠的浓度为40mg/mL，搅拌形成均匀溶液，将该溶液逐滴滴入100mL 30mg/mL的亚硫酸铁溶液中，使海藻酸钠与铁离子交联形成凝胶球，将该凝胶球在-40℃冷冻12h，再放在室温下解冻12h，反复冷解冻3次，使得明胶形成凝胶。将该双网络凝胶进行冷冻干燥形成气凝胶，将该气凝胶在H2保护气氛、铜基底催化下在800℃煅烧6h，获得三维网状石墨烯气凝胶。该凝胶比表面积高达800m2/g。
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，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。

Claims (31)

1.一种三维网状石墨烯气凝胶的制备方法，其特征在于，包括如下步骤：
(1)将聚合物和过渡金属盐溶于水中，得到混合溶液；其中，所述聚合物包括脂肪族醇类、琼脂或蛋白质；所述过渡金属盐包括铁、钴、铜、银、锰或镍盐；
(2)将步骤(1)得到的所述混合溶液密闭加热；
(3)将步骤(2)得到的产物先与海藻酸钠、羧甲基纤维素钠或壳聚糖的水溶液混合，后与过渡金属盐溶液混合，再反复冷解冻形成凝胶；
(4)将步骤(3)得到的凝胶在保护气氛、过渡金属基底催化下高温煅烧，即得到所述三维网状石墨烯气凝胶；其中，所述保护气氛为氮气、惰性气体或还原气体。
2.根据权利要求1所述的制备方法，其特征在于，所述脂肪族醇类为聚乙烯醇或聚乙二醇。
3.根据权利要求1所述的制备方法，其特征在于，所述蛋白质为明胶或丝素蛋白。
4.根据权利要求1所述的制备方法，其特征在于，步骤(1)中的聚合物浓度为0.01～1000mg/mL，过渡金属盐浓度为0.001～100mol/L。
5.根据权利要求4所述的制备方法，其特征在于，步骤(1)中的聚合物浓度为1～10mg/mL。
6.根据权利要求4所述的制备方法，其特征在于，步骤(1)中的过渡金属盐浓度为0.1～1mol/L。
7.根据权利要求1所述的制备方法，其特征在于，步骤(2)中的加热温度为50℃～400℃。
8.根据权利要求7所述的制备方法，其特征在于，步骤(2)中的加热温度为100～120℃。
9.根据权利要求8所述的制备方法，其特征在于，步骤(2)中的加热温度为120℃。
10.根据权利要求1所述的制备方法，其特征在于，步骤(2)中的加热时间为6～48h。
11.根据权利要求10所述的制备方法，其特征在于，步骤(2)中的加热时间为10～20h。
12.根据权利要求11所述的制备方法，其特征在于，步骤(2)中的加热时间为12h。
13.根据权利要求1所述的制备方法，其特征在于，步骤(3)中冷冻的温度为-80℃～0℃。
14.根据权利要求13所述的制备方法，其特征在于，步骤(3)中冷冻的温度为-80℃～-40℃。
15.根据权利要求14所述的制备方法，其特征在于，步骤(3)中冷冻的温度为-40℃。
16.根据权利要求1所述的制备方法，其特征在于，步骤(3)中冷解冻的反复次数为至少1次。
17.根据权利要求16所述的制备方法，其特征在于，步骤(3)中冷解冻的反复次数为3或4次。
18.根据权利要求1所述的制备方法，其特征在于，所述惰性气体包括氩气。
19.根据权利要求1所述的制备方法，其特征在于，所述还原气体包括氢气。
20.根据权利要求1所述的制备方法，其特征在于，步骤(4)中所述的过渡金属基底催化步骤中采用铁、钴、铜、银、锰或镍基底。
21.根据权利要求1所述的制备方法，其特征在于，步骤(4)中所述的高温煅烧温度为400～2000℃。
22.根据权利要求21所述的制备方法，其特征在于，步骤(4)中所述的高温煅烧温度为600～1000℃。
23.根据权利要求22所述的制备方法，其特征在于，步骤(4)中所述的高温煅烧温度为800℃。
24.根据权利要求1所述的制备方法，其特征在于，步骤(4)中所述的高温煅烧时间为1～24h。
25.根据权利要求24所述的制备方法，其特征在于，步骤(4)中所述的高温煅烧时间为1～8h。
26.根据权利要求25所述的制备方法，其特征在于，步骤(4)中所述的高温煅烧时间为2h。
27.一种通过如权利要求1～26任一项所述的制备方法制备得到的三维网状石墨烯气凝胶。
28.根据权利要求27所述的三维网状石墨烯气凝胶，其特征在于，所述三维网状石墨烯气凝胶具有高比表面积200～1000m2/g。
29.根据权利要求27所述的三维网状石墨烯气凝胶，其特征在于，所述三维网状石墨烯气凝胶具有优异的吸附性能，对水中100mg/L的四环素吸附去除率大于等于90％。
30.根据权利要求27所述的三维网状石墨烯气凝胶，其特征在于，所述三维网状石墨烯气凝胶具有优异的催化性能，对水中100mg/mL的环丙沙星通过非均相芬顿催化的去除率大于等于95％。
31.一种如权利要求27～30任一项所述的三维网状石墨烯气凝胶在环境和能源领域中的应用。
CN201811423244.5A 2018-11-26 2018-11-26 三维网状石墨烯气凝胶、其制备方法及其应用 Active CN109433154B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811423244.5A CN109433154B (zh) 2018-11-26 2018-11-26 三维网状石墨烯气凝胶、其制备方法及其应用

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811423244.5A CN109433154B (zh) 2018-11-26 2018-11-26 三维网状石墨烯气凝胶、其制备方法及其应用

Publications (2)

Publication Number Publication Date
CN109433154A CN109433154A (zh) 2019-03-08
CN109433154B true CN109433154B (zh) 2021-01-29

Family

ID=65554337

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811423244.5A Active CN109433154B (zh) 2018-11-26 2018-11-26 三维网状石墨烯气凝胶、其制备方法及其应用

Country Status (1)

Country Link
CN (1) CN109433154B (zh)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110117009B (zh) * 2019-05-27 2020-10-13 武汉大学 一种铁氮共掺杂磁性多孔石墨化纳米碳气凝胶的制备方法
CN112010288B (zh) * 2019-05-29 2022-04-01 中国科学院宁波材料技术与工程研究所 一种管状石墨烯气凝胶及其制备方法和应用
CN110560029B (zh) * 2019-09-16 2020-10-20 中国科学院生态环境研究中心 石墨烯基无金属芬顿催化剂、其制备方法及应用
CN111054305A (zh) * 2019-11-19 2020-04-24 中国科学院生态环境研究中心 一种石墨烯金属基气凝胶及其制备方法
CN112467111B (zh) * 2020-04-29 2023-05-26 重庆大学 一种导电碳基底负载石墨烯气凝胶复合电极及其制备方法
CN111499927B (zh) * 2020-06-24 2022-03-01 内蒙古科技大学 一种纤维素/丝素蛋白复合气凝胶长纤维及其制备方法
CN112076759B (zh) * 2020-09-08 2023-07-25 湖南农业大学 石墨毡阴极、其制备方法和应用
CN112047452A (zh) * 2020-09-15 2020-12-08 华东理工大学 一种净水用复合水凝胶及其制备方法和应用方法
CN113086967A (zh) * 2021-04-12 2021-07-09 北京化工大学 一种均匀的炭-氧化锰复合气凝胶电极材料的制备方法
CN113436905B (zh) * 2021-06-25 2022-10-04 中南林业科技大学 碳/氧化镍复合电极材料的制备方法
CN116062738B (zh) * 2022-12-30 2024-06-11 中国科学院福建物质结构研究所 一种二次增强石墨烯气凝胶及其制备方法和应用

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104477901B (zh) * 2014-12-16 2016-05-11 中国科学院宁波材料技术与工程研究所 一种石墨烯的制备方法及石墨烯
CN104743547B (zh) * 2015-03-06 2016-08-24 同济大学 一种三维石墨烯宏观体的制备方法
CN107189090A (zh) * 2017-06-28 2017-09-22 中国科学院生态环境研究中心 海藻酸盐‑聚乙烯醇纳米复合双网络凝胶及其制备方法
CN109529888B (zh) * 2018-11-26 2020-10-20 中国科学院生态环境研究中心 三维石墨烯基非均相芬顿催化剂、其制备方法及其应用

Also Published As

Publication number Publication date
CN109433154A (zh) 2019-03-08

Similar Documents

Publication Publication Date Title
CN109433154B (zh) 三维网状石墨烯气凝胶、其制备方法及其应用
Shu et al. Diverse metal–organic framework architectures for electromagnetic absorbers and shielding
Miao et al. Poly (dimethylsilylene) diacetylene-guided ZIF-based heterostructures for full Ku-band electromagnetic wave absorption
US11027259B2 (en) Preparation method for hollow molybdate composite microspheres and method for catalyzing ammonia borane hydrolysis to produce hydrogen
CN109208030B (zh) 一种金属氢氧化物-金属有机框架复合材料及其制备方法
Tong et al. Generalized green synthesis and formation mechanism of sponge-like ferrite micro-polyhedra with tunable structure and composition
Liu et al. Shape-and size-dependent catalysis activities of iron-terephthalic acid metal-organic frameworks
CN106744786B (zh) 一种金属-氮掺杂多孔碳微球的制备方法
CN107088388B (zh) 一种复合气凝胶材料、制备方法及其多功能再利用方法、多功能复合气凝胶材料和应用
KR101906043B1 (ko) 마이크로파를 이용한 탄소-금속유기골격구조(MOFs) 복합체 제조 방법
Song et al. Magnetic hard/soft nanocomposite ferrite aligned hollow microfibers and remanence enhancement
CN106957439B (zh) 基于含钴双金属氧化物无溶剂制备Co-MOF材料的方法
CN111825081B (zh) 一种石墨烯负载mof衍生物气凝胶及其制备方法
CN107418513B (zh) 一种石墨烯泡沫负载纳米Fe3O4磁性粒子复合吸波材料及其制备方法
CN108187712B (zh) 一种非金属氮化硼催化剂及制备和应用与再生方法
CN108997971A (zh) ZIF-67还原氧化石墨烯基吸波复合材料(CoC-rGo)的制备方法
CN112087939B (zh) 一种FeCoNi@C/碳纳米管磁性复合吸波材料与应用
CN109529888B (zh) 三维石墨烯基非均相芬顿催化剂、其制备方法及其应用
Han et al. Research progresses in the preparation of Co-based catalyst derived from Co-MOFs and application in the catalytic oxidation reaction
Ali et al. A novel route to the formation of 3D nanoflower-like hierarchical iron oxide nanostructure
Tian et al. Recent advances in the template-confined synthesis of two-dimensional materials for aqueous energy storage devices
CN102963938A (zh) 一种尖晶石铁氧体/CNx纳米复合材料及其制备方法
CN108996557B (zh) 一种空心球结构氧化镍/氧化铜复合纳米材料及其制备方法
CN105834446A (zh) 一种超薄层状NiO-CoOx纳米片负载NiCo纳米粒子复合材料的合成方法
CN110451465B (zh) 一种海胆状氮化硼纳米球-纳米管分级结构及其制备方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant