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不同价态Ce-MOF衍生材料的吸附除磷性能及机理比较

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何皎洁, 徐雨虹, 杨悦, 杨利伟. 不同价态Ce-MOF衍生材料的吸附除磷性能及机理比较[J]. 环境化学, 2020, (3): 715-725. doi: 10.7524/j.issn.0254-6108.2019102502
引用本文: 何皎洁, 徐雨虹, 杨悦, 杨利伟. 不同价态Ce-MOF衍生材料的吸附除磷性能及机理比较[J]. 环境化学, 2020, (3): 715-725. doi: 10.7524/j.issn.0254-6108.2019102502
shu
HE Jiaojie, XU Yuhong, YANG Yue, YANG Liwei. The influence of valence states for Ce-MOF derived nanocomposites on the capability of phosphate adsorption and the mechanisms[J]. Environmental Chemistry, 2020, (3): 715-725. doi: 10.7524/j.issn.0254-6108.2019102502
Citation: HE Jiaojie, XU Yuhong, YANG Yue, YANG Liwei. The influence of valence states for Ce-MOF derived nanocomposites on the capability of phosphate adsorption and the mechanisms[J]. Environmental Chemistry, 2020, (3): 715-725. doi: 10.7524/j.issn.0254-6108.2019102502
shu

不同价态Ce-MOF衍生材料的吸附除磷性能及机理比较

  • 1. 长安大学建筑工程学院, 西安, 710061;

  • 2. 住房与城乡建设部给水排水重点实验室, 西安, 710061

    • 通讯作者: 杨利伟, E-mail: yanglw@chd.edu.cn
  • 基金项目:

    国家自然科学基金（51808043）和中央高校基本科研业务项目（自然科学类）（300102288301）资助.

The influence of valence states for Ce-MOF derived nanocomposites on the capability of phosphate adsorption and the mechanisms

  • 1. School of Civil Engineering, Chang'an University, Xi'an, 710061, China;

  • 2. Key Laboratory of Water Supply & Sewage Engineering of Ministry of Housing and Urban-rural Development, Xi'an, 710061, China

    • Corresponding author: YANG Liwei, yanglw@chd.edu.cn
  • Fund Project: Supported by the National Natural Science Foundation of China (51808043) and Central University Basic Research Business Project(Natural Science)(300102288301).

  • 摘要: 通过在N2气氛中的热处理，从Ce-MOF中衍生出一系列多级的微/纳米铈基复合材料.Ce-MOF在空气中完全分解形成二氧化铈，价态由三价转变为四价.而在N2中较低温度（400℃或500℃）下煅烧会形成稳定的部分热解的Ce-MOF（N），具有较高的Ce（Ⅲ）含量.与完全分解的产物相比，虽然完全分解的产物具有较高的比表面积，但是部分分解的样品对磷酸盐的吸附效果是完全分解产物的2-4倍.这种差异证明铈基材料的不同价态对除磷性能有显著影响，相比于四价铈离子，三价铈在与磷酸盐结合中起主要作用.与Ce-MOF（A）相比，Ce-MOF（N）是一种高Ce（Ⅲ）含量的铈基纳米材料，其饱和吸附容量为187.2 mg·g-1，吸附速度快，pH适用范围极广，为pH 2-12，并且在竞争阴离子存在下也对磷酸盐具有很高的选择性.与此同时，相比于常用的金属盐吸附剂，Ce-MOF（N）在碱性条件下具有明显增强的磷酸盐吸附能力.这是因为表面Ce（Ⅲ）的部分水解带来了更多的羟基，增加了磷酸根离子交换的活性位点.此外，通过分析FTIR、XPS、XRD和Zeta电位，Ce（Ⅲ）样品对磷酸根的吸附机理主要为静电吸引，离子交换和表面沉积，而对于完全分解的铈基材料Ce-MOF（A）静电吸引是主要机理.
    Abstract: Through heat treatment in N2 atmosphere, a series of multi-stage micro/nano cerium matrix composites were derived from Ce-MOF. Ce-MOF completely decomposes in air to form cerium dioxide, and the valence state changed from trivalent to tetravalent. However, calcination at a lower temperature (400℃ or 500℃) in N2 would result in a stable partial pyrolysis of Ce-MOF(N) with a higher Ce(Ⅲ) content. Compared with the completely decomposed product, although the completely decomposed product had a higher specific surface area, the phosphate adsorption effect of the partially decomposed sample was 2-4 times of that of the completely decomposed product. This difference showed that the different valence states of Cerium based materials had a significant impact on the phosphorus removal performance. Compared with cerium ions(Ⅳ), cerium ions(Ⅲ) played a major role in the combination with phosphate. Compared with Ce-MOF(A), Ce-MOF(N) was a kind of Ce based nano material with high Ce(Ⅲ) content. Its saturated adsorption capacity was 187.2 mg·g-1, and the adsorption speed was fast. The pH range was very wide, from 2 to 12, and it also had high selectivity for phosphate in the presence of competitive anions. At the same time, Ce-MOF(N) had significantly enhanced phosphate adsorption capacity under alkaline conditions compared with the commonly used metal salt adsorbents. This was because the partial hydrolysis of Ce(Ⅲ) on the surface brings more hydroxyl groups and increases the active sites of phosphate ion exchange. In addition, through the analysis of FTIR, XPS, XRD and zeta potential, the adsorption mechanism of Ce(Ⅲ) on phosphate was mainly electrostatic attraction, ion exchange and surface deposition, while the electrostatic attraction of Ce-MOF(A) was the main mechanism.
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  • [1] WU M Y, YU W Z, QU J H, et al. The variation of flocs activity during floc breakage and aging, adsorbing phosphate, humic acid and clay particles[J]. Water Research, 2019,155:131-141.
    [2] BRAUN J C A, BORBA C E., GODINHO M, et al. Phosphorus adsorption in Fe-loaded activated carbon:Two-site monolayer equilibrium model and phenomenological kinetic description[J]. Chemical Engineering Journal, 2018, 361:751-763.
    [3] ZHANG Z R,YAN L G,YU H Q, et al. Adsorption of phosphate from aqueous solution by vegetable biochar/layered double oxides:Fast removal and mechanistic studies[J]. Bioresource Technology,2019,284:65-71.
    [4] YANG F, ZHANG S S, SUN Y Q, et al. Assembling biochar with various layered double hydroxides for enhancement of phosphorus recovery[J]. Journal of Hazardous Materials,2019,365:665-673.
    [5] HAO H, WANG Y, SHI B. NaLa(CO3)2 hybridized with Fe3O4 for efficient phosphate removal:Synthesis and adsorption mechanistic study[J]. Water Research,2019,155:1-11.
    [6] HE J J, WANG W, SUN F L, et al. Highly efficient phosphate scavenger based on well-dispersed La(OH)3 nanorods in polyacrylonitrile nanofibers for nutrient-starvation antibacteria[J]. ACS nano, 2015, 9:9292-9302.
    [7] HUA G, SALO M W, SCHMIT C G, et al. Nitrate and phosphate removal from agricultural subsurface drainage using laboratory woodchip bioreactors and recycled steel byproduct filters[J]. Water Research, 2016,102:180-189.
    [8] FANG L, LIU R, LI J, et al. Magnetite/Lanthanum hydroxide for phosphate sequestration and recovery from lake and the attenuation effects of sediment particles[J]. Water Research, 2018, 130:243-254.
    [9] BUI T H, HONG S P, YOON J. Development of nanoscale zirconium molybdate embedded anion exchange resin for selective removal of phosphate[J]. Water Research, 2018, 134:22-31.
    [10] TIAN Y, HE W, LIANG D, et al. Effective phosphate removal for advanced water treatment using low energy, migration electric-field assisted electrocoagulation[J]. Water Research,2018,138:129-136.
    [11] GAO Y, ZHANG W, GAO B, et al. Highly efficient removal of nitrogen and phosphorus in an electrolysis-integrated horizontal subsurface-flow constructed wetland amended with biochar[J]. Water Research, 2018, 139:301-310.
    [12] GENG Y, WANG Y, PAN X, et al. Electricity generation and in situ phosphate recovery from enhanced biological phosphorus removal sludge by electrodialysis membrane bioreactor[J]. Bioresource Technology, 2018, 247:471-476.
    [13] HASHIM K S., KHADDAR R AL, JASIM N, et al. Electrocoagulation as a green technology for phosphate removal from river water[J]. Separation and Purification Technology, 2019, 210:135-144.
    [14] ZHOU K, WU B R, SU L G, et al. Enhanced phosphate removal using nanostructured hydrated ferric-zirconium binary oxide confined in a polymeric anion exchanger[J]. Chemical Engineering Journal, 2018, 345:640-647.
    [15] SHAN S, TANG H, ZHAO Y, et al. Highly porous zirconium-crosslinked graphene oxide/alginate aerogel beads for enhanced phosphate removal[J]. Chemical Engineering Journal, 2019, 359:779-789.
    [16] CHEN L, LI Y, SUN Y, et al. La(OH)3 loaded magnetic mesoporous nanospheres with highly efficient phosphate removal properties and superior pH stability[J]. Chemical Engineering Journal, 2019, 360:342-348.
    [17] LI M, LIU J, XU Y, et al. Phosphate adsorption on metal oxides and metal hydroxides:A comparative review[J]. Environmental Reviews, 2016:er-2015-0080.
    [18] ZHANG Y, PAN B, SHAN C, et al. enhanced phosphate removal by nanosized hydrated La(Ⅲ) oxide confined in crosslinked polystyrene networks[J]. Environmental Science & Technology, 2016, 50:1447-1454.
    [19] KONG L, TIAN Y, WANG Y, et al. Periclase-induced generation of flowerlike clay-based layered double hydroxides:A highly efficient phosphate scavenger and solid-phase fertilizer[J]. Chemical Engineering Journal, 2019, 359:902-913.
    [20] LIU R, CHI L, WANG X, et al. Effective and selective adsorption of phosphate from aqueous solution via trivalent-metals-based amino-MIL-101 MOFs[J]. Chemical Engineering Journal, 2019, 357:159-168.
    [21] SU Y, YANG W, SUN W, et al. Synthesis of mesoporous cerium-zirconium binary oxide nanoadsorbents by a solvothermal process and their effective adsorption of phosphate from water[J]. Chemical Engineering Journal, 2015, 268:270-279.
    [22] NIE G, WU L, DU Y, et al. Efficient removal of phosphate by a millimeter-sized nanocomposite of titanium oxides encapsulated in positively charged polymer[J]. Chemical Engineering Journal, 2019, 360:1128-1136.
    [23] MITROGIANNIS D, PSYCHOYOU M, BAZIOTIS I, et al. Removal of phosphate from aqueous solutions by adsorption onto Ca(OH)2 treated natural clinoptilolite[J]. Chemical Engineering Journal, 2017, 320:510-522.
    [24] PENG B, CUI J, WANG Y, et al. CeO2-x/C/rGO nanocomposites derived from Ce-MOF and graphene oxide as robust platform for highly sensitive uric acid detection[J]. Nanoscale, 2018,10:1939-1945.
    [25] MONTINI T, MELCHIONNA M, MONAI M, et al. Fundamentals and catalytic applications of CeO2 based materials[J]. Chemical Reviews, 2016, 116:5987-6041.
    [26] HE J, WANG W, SHI R, et al. High speed water purification and efficient phosphate rejection by active nanofibrous membrane for microbial contamination and regrowth control[J]. Chemical Engineering Journal, 2018, 337:428-435.
    [27] HE J, WANG W, SHI W, et al. La2O3 nanoparticle/polyacrylonitrile nanofibers for bacterial inactivation based on phosphate control[J]. RSC Adv, 2016, 6:99353-99360.
    [28] DAHLE J T, LIVI K, ARAI Y. Effects of pH and phosphate on CeO2 nanoparticle dissolution[J]. Chemosphere, 2015, 119:1365-1371.
    [29] LI C, ZHANG Y, WANG X, et al. The synthesis and characterization of hydrous cerium oxide nanoparticles loaded on porous silica micro-sphere as novel and efficient adsorbents to remove phosphate radicals from water[J]. Microporous and Mesoporous Materials, 2019, 279:73-81.
    [30] YU Y,ZHANG C, YANG L, et al. Cerium oxide modified activated carbon as an efficient and effective adsorbent for rapid uptake of arsenate and arsenite:Material development and study of performance and mechanisms[J]. Chemical Engineering Journal, 2017,315:630-638.
    [31] BOUCHAUD B, BALMAIN J, BONNET G, et al. pH-distribution of cerium species in aqueous systems[J]. Journal of Rare Earths, 2012, 30:559-562.
    [32] ZHANG X, SUN F, HE J, et al. Robust phosphate capture over inorganic adsorbents derived from lanthanum metal organic frameworks[J]. Chemical Engineering Journal, 2017, 326:1086-1094.
    [33] ZHANG X, HOU F, LI H, et al. A strawsheave-like metal organic framework Ce-BTC derivative containing high specific surface area for improving the catalytic activity of CO oxidation reaction[J]. Microporous Mesoporous Mater,2018,259:211-219.
    [34] 孙风莲. La2O2CO3海胆状微球吸附剂制备及除磷性能研究[D].哈尔滨:哈尔滨工业大学,2016. SUN F L. Preparation of La2O2CO3

    sea urchin microsphere adsorbent and study on its posphorus removal performance[D]. Harbin:Harbin Institute of Technology,2016(in Chinese).

    [35] CHEN G, GUO Z, ZHAO W, et al. Design of porous/hollow structured ceria by partial thermal decomposition of Ce-MOF and selective etching[J]. ACS Applied Materials & Interfaces, 2017, 9:39594-39601.
    [36] XIONG Y, CHEN S, YE F, et al. Synthesis of a mixed valence state Ce-MOF as an oxidase mimetic for the colorimetric detection of biothiols[J]. Chem Commun,2015, 51:4635-4638.
    [37] KONG L, TIAN Y, LI N, et al. Highly-effective phosphate removal from aqueous solutions by calcined nano-porous palygorskite matrix with embedded lanthanum hydroxide[J]. Applied Clay Science, 2018, 162:507-517.
    [38] QIU H, YE M, ZENG Q, et al. Fabrication of agricultural waste supported UiO-66 nanoparticles with high utilization in phosphate removal from water[J]. Chemical Engineering Journal, 2019,360:621-630.
    [39] XIE F, WU F, LIU G, et al. Removal of phosphate from eutrophic lakes through adsorption by in situ formation of magnesium hydroxide from diatomite[J]. Environ. Sci. Technol., 2013,48:582-590.
    [40] LIU H, WANG X, ZHAI G, et al. Preparation of activated carbon from lotus stalks with the mixture of phosphoric acid and pentaerythritol impregnation and its application for Ni(Ⅱ) sorption[J].Chemical Engineering Journal, 2012, 209:155-162.
    [41] LIU B, CHEN X, ZHENG H, et al. Rapid and efficient removal of heavy metal and cationic dye by carboxylate-rich magnetic chitosan flocculants:Role of ionic groups[J]. Carbohydrate Polymers, 2018, 181:327-336.
    [42] CHEN M, HUO C, LI Y, et al. Selective adsorption and efficient removal of phosphate from aqueous medium with graphene-Lanthanum composite[J]. ACS Sustainable Chem Eng, 2015,4:1296-1302.
    [43] JUNG K, LEE S, LEE Y J. Synthesis of novel magnesium ferrite (MgFe2O4)/biochar magnetic composites and its adsorption behavior for phosphate in aqueous solutions[J]. Bioresource Technology, 2017,245:751-759.
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  • 收稿日期:  2019-10-25

不同价态Ce-MOF衍生材料的吸附除磷性能及机理比较

    通讯作者: 杨利伟, E-mail: yanglw@chd.edu.cn
  • 1. 长安大学建筑工程学院, 西安, 710061;
  • 2. 住房与城乡建设部给水排水重点实验室, 西安, 710061
  • 收稿日期:  2019-10-25
基金项目:

国家自然科学基金（51808043）和中央高校基本科研业务项目（自然科学类）（300102288301）资助.

摘要: 通过在N2气氛中的热处理，从Ce-MOF中衍生出一系列多级的微/纳米铈基复合材料.Ce-MOF在空气中完全分解形成二氧化铈，价态由三价转变为四价.而在N2中较低温度（400℃或500℃）下煅烧会形成稳定的部分热解的Ce-MOF（N），具有较高的Ce（Ⅲ）含量.与完全分解的产物相比，虽然完全分解的产物具有较高的比表面积，但是部分分解的样品对磷酸盐的吸附效果是完全分解产物的2-4倍.这种差异证明铈基材料的不同价态对除磷性能有显著影响，相比于四价铈离子，三价铈在与磷酸盐结合中起主要作用.与Ce-MOF（A）相比，Ce-MOF（N）是一种高Ce（Ⅲ）含量的铈基纳米材料，其饱和吸附容量为187.2 mg·g-1，吸附速度快，pH适用范围极广，为pH 2-12，并且在竞争阴离子存在下也对磷酸盐具有很高的选择性.与此同时，相比于常用的金属盐吸附剂，Ce-MOF（N）在碱性条件下具有明显增强的磷酸盐吸附能力.这是因为表面Ce（Ⅲ）的部分水解带来了更多的羟基，增加了磷酸根离子交换的活性位点.此外，通过分析FTIR、XPS、XRD和Zeta电位，Ce（Ⅲ）样品对磷酸根的吸附机理主要为静电吸引，离子交换和表面沉积，而对于完全分解的铈基材料Ce-MOF（A）静电吸引是主要机理.

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