WO2021143275A1 - Adsorbant à base d'oxyde de graphène, procédé de préparation associé et application associée - Google Patents

Adsorbant à base d'oxyde de graphène, procédé de préparation associé et application associée Download PDF

Info

Publication number
WO2021143275A1
WO2021143275A1 PCT/CN2020/124994 CN2020124994W WO2021143275A1 WO 2021143275 A1 WO2021143275 A1 WO 2021143275A1 CN 2020124994 W CN2020124994 W CN 2020124994W WO 2021143275 A1 WO2021143275 A1 WO 2021143275A1
Authority
WO
WIPO (PCT)
Prior art keywords
graphene oxide
hydrotalcite
preparation
composite material
prepared
Prior art date
Application number
PCT/CN2020/124994
Other languages
English (en)
Chinese (zh)
Inventor
戈明亮
席壮壮
Original Assignee
华南理工大学
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 华南理工大学 filed Critical 华南理工大学
Publication of WO2021143275A1 publication Critical patent/WO2021143275A1/fr

Links

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
    • 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
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
    • 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
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/42—Materials comprising a mixture of inorganic materials
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/48—Sorbents characterised by the starting material used for their preparation
    • B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
    • 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
    • C02F2101/308—Dyes; Colorants; Fluorescent agents

Definitions

  • the invention relates to the field of preparation of graphene oxide composite materials, in particular to an adsorbent based on graphene oxide and a preparation method and application thereof.
  • Graphene oxide Oxide is the oxidation product of graphene. It can form negatively charged flakes in water. It has a large specific surface area and contains a variety of active oxygen-containing groups, which can provide more active sites. Therefore, graphene oxide It can be used as an adsorbent to remove various pollutants in wastewater,
  • Hydrotalcite is also called layered double hydroxide (Layered double hydroxides, LDH), it is a naturally occurring layered clay material.
  • the microstructure of LDH mainly includes the main layer plate and the interlayer anion.
  • the main layer plate has a positive charge and the interlayer anion has a negative charge.
  • the metal type and charge density on the main layer board are adjustable, and the interlayer anions are also exchangeable.
  • Graphene oxide is very easy to agglomerate, reducing its adsorption effect.
  • hydrotalcite can be combined with graphene oxide to prevent the agglomeration of graphene oxide and enhance its adsorption capacity.
  • Garcia-Gallastegui et al. (Garcia-Gallastegui A, Iruretagoyena D, Gouvea V, et al. Graphene oxide as support for layered double hydroxides: enhancing the CO2 adsorption capacity[J]. Chemistry of Materials.
  • the in-situ growth method requires the preparation of hydrotalcite in the presence of graphene oxide. Therefore, the graphene oxide and hydrotalcite in the prepared composite material have defects; and the concentration of graphene oxide dispersion is relatively low, usually Under the circumstances, 1g of graphene oxide needs 1L of water to disperse well, and when preparing hydrotalcite, less water is required. Normally, 1L of water can prepare 100g of hydrotalcite, so the composite material prepared by in-situ growth method is oxidized The graphene content is small, and the ratio of graphene oxide to hydrotalcite cannot be well controlled; secondly, the in-situ growth method is complicated to operate and requires many experimental conditions.
  • the purpose of the present invention is to provide a graphene oxide-based adsorbent and a preparation method and application thereof in view of the high cost of the current graphene oxide composite material and the difficulty of removal after adsorption.
  • the adsorbent provided by the invention is a graphene oxide-hydrotalcite composite material prepared by a co-precipitation method, and can be applied to the field of adsorbing water pollutants. The method specifically peels and disperses graphene oxide in water, adds hydrotalcite, and stirs vigorously after ultrasonic dispersion.
  • the graphene oxide can be peeled into negatively charged flakes in water, and the main layer of hydrotalcite is positively charged, which means graphite oxide
  • the olefin and hydrotalcite laminates can be self-assembled to prepare graphene oxide-hydrotalcite composites through electrostatic interaction.
  • the method for preparing a graphene oxide-based adsorbent provided by the present invention includes the following steps:
  • step (2) Adding hydrotalcite to the graphene oxide solution described in step (1), ultrasonically treating, and then mechanically stirring to obtain a mixed solution;
  • step (3) The layering phenomenon occurs after the mixed solution of step (2) is allowed to stand, the graphene oxide and hydrotalcite are co-precipitated, the supernatant is removed, and the precipitate is vacuum dried and ground to obtain the graphene oxide based adsorption Agent.
  • the concentration of the graphene oxide solution in step (1) is 1 mg/ml-4 mg/ml.
  • the concentration of the graphene oxide solution is 2 mg/ml.
  • the graphene oxide in step (1) is prepared by the Hummers method.
  • the time of the ultrasonic treatment in step (1) is 12h-48h.
  • the time of the ultrasonic treatment in step (1) is 24h.
  • the hydrotalcite in step (2) is a hydrotalcite artificially synthesized by a hydrothermal method.
  • hydrotalcite in step (2) is a magnesia-aluminum hydrotalcite.
  • the mass of the hydrotalcite in step (2) is 4-19 times the mass of the graphene oxide in step (1).
  • the mass of the added hydrotalcite is 9 times the mass of graphene oxide.
  • step (2) the time of ultrasonic treatment in step (2) is 1-4 h, and the time of mechanical stirring is 2-8 h.
  • the time of the ultrasonic treatment in step (2) is 1 h.
  • the mechanical stirring time in step (2) is 2h.
  • the standing time in step (3) is 12-24h.
  • the standing time in step (3) is 24h.
  • the present invention provides a graphene oxide-based adsorbent obtained by the above preparation method.
  • Graphene oxide can be exfoliated in water to form negatively charged flakes, while the main hydrotalcite layer has a positive charge.
  • the main layer of graphene oxide and hydrotalcite can be prepared by electrostatic interaction and self-assembly to obtain a graphene oxide-hydrotalcite composite Material.
  • Graphene oxide adsorbs methylene blue mainly by using its larger specific surface area. Hydrotalcite has no adsorption effect on methylene blue, and graphene oxide is very easy to agglomerate, which will reduce the adsorption effect.
  • the adsorption effect of composite materials mainly comes from graphene oxide. After the composite material is formed, the agglomeration of graphene oxide is suppressed, so its adsorption effect is better than that of agglomerated graphene oxide.
  • the present invention prepares the graphene oxide-hydrotalcite composite material by the co-precipitation method. On the one hand, it can inhibit the agglomeration of graphene oxide. On the other hand, the hydrotalcite can be co-precipitated with graphene oxide, which is easily removed after adsorption and does not produce new Pollution. Therefore, the adsorption effect of the graphene oxide-hydrotalcite composite material is better than that of the agglomerated graphene oxide. The most important thing is that the graphene oxide-hydrotalcite composite material can greatly reduce the use cost of graphene oxide.
  • the present invention first prepares graphene oxide and hydrotalcite separately, and then peels off the layered graphene oxide and hydrotalcite through ultrasonic and stirring treatment.
  • the graphene oxide and hydrotalcite will self-assemble together due to electrostatic action, and then co-precipitate. This method It is easy to operate, does not damage the structure of graphene oxide and hydrotalcite in the process of preparing the composite material, and can accurately control the ratio of graphene oxide to hydrotalcite in the composite material.
  • the present invention has the following advantages and beneficial effects:
  • the graphene oxide-based adsorbent provided by the present invention has a graphene oxide content of only 5%-25%, but its adsorption efficiency is much higher than graphene oxide or hydrotalcite, which reduces the use cost of graphene oxide as an adsorbent The most important thing is that after the adsorption is completed, the graphene oxide-based adsorbent will naturally precipitate, without complicated operations such as centrifugation, which improves its practical application value.
  • Figure 1 is an infrared spectrogram of the graphene oxide-based adsorbent prepared in Example 1;
  • 2 is a bar graph showing the removal efficiency of hydrotalcite, graphene oxide, and graphene oxide-based adsorbents for methylene blue in the examples.
  • a method for preparing a graphene oxide-based adsorbent the specific steps are as follows:
  • step (2) Leave the mixed solution in step (2) for 24 hours. It can be observed that the graphene oxide and hydrotalcite co-precipitate, and the solution is stratified. Discard the supernatant, vacuum dry and grind the lower layer of the precipitate to obtain the result.
  • the graphene oxide-based adsorbent prepared in Example 1 is used in the field of adsorbing water pollutants. This example is methylene blue. The specific steps are as follows:
  • FIG. 2 The removal efficiency of methylene blue by hydrotalcite, graphene oxide and graphene oxide-based adsorbents is shown in Figure 2.
  • LDH stands for hydrotalcite
  • GO stands for graphene oxide
  • GO-LDH graphene oxide-based adsorption. It can be seen from Figure 2 that the removal rate of methylene blue by the graphene oxide-based adsorbent is 98.02%, which is much higher than the removal rate of graphene oxide for methylene blue of 90.53% and hydrotalcite of 28.51 for methylene blue. %.
  • a method for preparing a graphene oxide-based adsorbent the specific steps are as follows:
  • step (3) The mixed solution described in step (2) is allowed to stand for 12 hours. It can be observed that the graphene oxide and hydrotalcite are co-precipitated, and the solution is stratified. The supernatant is discarded, the lower sediment is vacuum dried, and the lower sediment is ground. The adsorbent based on graphene oxide.
  • the graphene oxide-based adsorbent prepared in Example 2 also has a good removal effect on methylene blue, as shown in FIG. 2.
  • a method for preparing a graphene oxide-based adsorbent the specific steps are as follows:
  • step (3) Leave the mixed solution in step (2) for 18 hours. It can be observed that the graphene oxide and hydrotalcite co-precipitate and the solution is stratified. Discard the supernatant, vacuum dry and grind the lower layer of the precipitate to obtain the result.
  • the graphene oxide-based adsorbent prepared in Example 3 also has a good removal effect on methylene blue, as shown in FIG. 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Analytical Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Water Treatment By Sorption (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

L'invention concerne un adsorbant à base d'oxyde de graphène, un procédé de préparation associé et une application associée. L'adsorbant selon la présente invention présente un bon effet d'adsorption sur les polluants de l'eau. Le procédé comprend les étapes suivantes : la dispersion par ultrasons d'un oxyde de graphène préparé par un procédé de Hummers dans de l'eau ; puis l'ajout d'hydrotalcite préparé par un procédé de synthèse hydrothermique dans une solution aqueuse d'oxyde de graphène ayant une bonne dispersité et l'agitation de celle-ci ; l'intercalation d'oxyde de graphène chargé négativement dans des couches d'hydrotalcite au moyen de l'effet électrostatique, et la co-précipitation avec de l'hydrotalcite, le repos pour la stratification, le versement d'un surnageant, et le séchage des précipités sous-jacents pour obtenir un matériau composite d'oxyde de graphène-hydrotalcite, de telle sorte que le phénomène d'agglomération de l'oxyde de graphène peut être efficacement réduit. Selon le procédé de préparation, l'hydrotalcite est ajouté dans la solution d'oxyde de graphène, le fonctionnement est simple, le matériau composite d'oxyde de graphène-hydrotalcite est préparé, et comme le phénomène d'agglomération de l'oxyde de graphène dans le matériau composite est inhibé, la performance d'adsorption du matériau composite est meilleure.
PCT/CN2020/124994 2020-01-15 2020-10-30 Adsorbant à base d'oxyde de graphène, procédé de préparation associé et application associée WO2021143275A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202010039620.1 2020-01-15
CN202010039620.1A CN111203178A (zh) 2020-01-15 2020-01-15 一种基于氧化石墨烯的吸附剂及其制备方法与应用

Publications (1)

Publication Number Publication Date
WO2021143275A1 true WO2021143275A1 (fr) 2021-07-22

Family

ID=70780752

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2020/124994 WO2021143275A1 (fr) 2020-01-15 2020-10-30 Adsorbant à base d'oxyde de graphène, procédé de préparation associé et application associée

Country Status (2)

Country Link
CN (1) CN111203178A (fr)
WO (1) WO2021143275A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114988401A (zh) * 2022-05-16 2022-09-02 南通赛可特电子有限公司 一种pcb板改性氧化石墨烯直接黑孔化的方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111203178A (zh) * 2020-01-15 2020-05-29 华南理工大学 一种基于氧化石墨烯的吸附剂及其制备方法与应用
CN112076753B (zh) * 2020-09-08 2021-09-17 浙江中科环境股份有限公司 一种印染废水用处理剂及其制备方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013132259A1 (fr) * 2012-03-09 2013-09-12 Bio Nano Consulting Aérogels/xérogels de graphène et d'oxyde de graphène pour la capture de co2
US20170266639A1 (en) * 2016-03-15 2017-09-21 Vaon, Llc Graphene-containing nanocomposite materials for sequestration of carbon dioxide
CN109775794A (zh) * 2019-01-29 2019-05-21 南昌大学 一种ldh处理有机废水后的废弃物的回收方法及其产品和用途
CN111203178A (zh) * 2020-01-15 2020-05-29 华南理工大学 一种基于氧化石墨烯的吸附剂及其制备方法与应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013132259A1 (fr) * 2012-03-09 2013-09-12 Bio Nano Consulting Aérogels/xérogels de graphène et d'oxyde de graphène pour la capture de co2
US20170266639A1 (en) * 2016-03-15 2017-09-21 Vaon, Llc Graphene-containing nanocomposite materials for sequestration of carbon dioxide
CN109775794A (zh) * 2019-01-29 2019-05-21 南昌大学 一种ldh处理有机废水后的废弃物的回收方法及其产品和用途
CN111203178A (zh) * 2020-01-15 2020-05-29 华南理工大学 一种基于氧化石墨烯的吸附剂及其制备方法与应用

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
FENG, GUANGJING: "Preparation of ZnAl-LDHs/GO Nanocomposites and Its Application in Removal of Chromium Ion from Aqueous Solutions", MASTER'S DISSERTATION OF XIAMEN UNIVERSITY, 1 May 2017 (2017-05-01), pages 1 - 87, XP055828719 *
LIN YAJIE: "Graphene/Layered Double Hydroxides Nanocomposites: A review of Recent Progress in Environmental Remediation", ENVIRONMENT AND SUSTAINABLE DEVELOPMENT, vol. 43, no. 3, 30 May 2017 (2017-05-30), pages 95 - 99, XP055828726, ISSN: 1673-288x, DOI: 10.19758/j.cnki.issn1673-288x.2017.03.025 *
WANG LEI, WANG DONG, DONG XIN YI, ZHANG ZHI JUN, PEI XIAN FENG, CHEN XIN JIANG, CHEN BIAO, JIN JIAN: "Layered assembly of graphene oxide and Co–Al layered double hydroxide nanosheets as electrode materials for supercapacitors", CHEMICAL COMMUNICATIONS, vol. 47, no. 12, 15 February 2011 (2011-02-15), pages 3556 - 3558, XP055828728, ISSN: 1359-7345, DOI: 10.1039/c0cc05420h *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114988401A (zh) * 2022-05-16 2022-09-02 南通赛可特电子有限公司 一种pcb板改性氧化石墨烯直接黑孔化的方法

Also Published As

Publication number Publication date
CN111203178A (zh) 2020-05-29

Similar Documents

Publication Publication Date Title
WO2021143275A1 (fr) Adsorbant à base d'oxyde de graphène, procédé de préparation associé et application associée
Asfaram et al. Experimental design and modeling of ultrasound assisted simultaneous adsorption of cationic dyes onto ZnS: Mn-NPs-AC from binary mixture
RezaeiKalantary et al. Adsorption and magnetic separation of lead from synthetic wastewater using carbon/iron oxide nanoparticles composite
Xu et al. 3D graphene aerogel composite of 1D-2D Nb2O5-g-C3N4 heterojunction with excellent adsorption and visible-light photocatalytic performance
Hu et al. Characteristics of manganese-coated sand using SEM and EDAX analysis
Zhou et al. Preparation of Fe 3 O 4-embedded graphene oxide for removal of methylene blue
CN105622960B (zh) 一种羧甲基壳聚糖/氧化石墨烯复合水凝胶及其制备与应用
US20130079223A1 (en) Method for preparing mesoporous carbon having iron oxide nanoparticles
WO2012062110A1 (fr) Procédé de préparation d'un composite phosphate de fer lithié/carbone pour pile lithium-ion
CN101643261B (zh) 一种控藻红土复合絮凝剂及其制备方法与应用
WO2016192311A1 (fr) Matériau composite fer-manganèse creux préparé par un procédé à gabarit de gravure et son application
Luo et al. Application of enteromorpha polysaccharides as coagulant aid in the simultaneous removal of CuO nanoparticles and Cu2+: Effect of humic acid concentration
CN106904705A (zh) 一种高效可循环的酸性含As(V)废水处理方法
Wu et al. Graphene nanosheets decorated with tunable magnetic nanoparticles and their efficiency of wastewater treatment
Naeem et al. Synthesis, characterization and adsorption studies of h-BN crystal for efficient removal of Cd2+ from aqueous solution
Lu et al. Three-dimensional electro-Fenton degradation of ciprofloxacin catalyzed by CuO doped red mud particle electrodes: Electrodes preparation, kinetics and mechanism
Han et al. Research on the removal of Cr (VI) ions from wastewater by Mg/Al-layered double oxides
CN113493225A (zh) 一种Co/Fe层状双金属氢氧化物纳米片的制备方法及应用
CN107868261A (zh) 一种羧甲基壳聚糖/氧化石墨烯复合水凝胶及其制备与应用
WO2023032811A1 (fr) Procédé de récupération de métal à partir d'une matière à teneur en éléments métalliques
Li et al. Preparation of silica/reduced graphene oxide nanosheet composites for removal of organic contaminants from water
CN111792697B (zh) 磁性焦糖化碳纳米材料在去除水体中重金属的应用
CN106693886A (zh) 一种用于地下水处理的磁性纳米高岭土的制备方法
CN113398896A (zh) 聚丙烯酸钠分散硫化亚铁插层层状双氢氧化物的制备方法
CN108325504B (zh) 一种天然层状硅酸盐纳米微粒与生物炭二级吸附去除阳离子染料的方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 20913783

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

32PN Ep: public notification in the ep bulletin as address of the adressee cannot be established

Free format text: NOTING OF LOSS OF RIGHTS PURSUANT TO RULE 112(1) EPC (EPO FORM 1205A DATED 09.11.2022)

122 Ep: pct application non-entry in european phase

Ref document number: 20913783

Country of ref document: EP

Kind code of ref document: A1