层状双金属氢氧化物形成机理的研究现状

doi:10.16085/j.issn.1000-6613.2017-0779

摘要/Abstract

摘要： 近年来，层状双金属氢氧化物（LDH）凭借特殊的层状结构、极强的可调控性能、优异的环境兼容性及显著的应用效果等特点，在环保、催化、储能、传感等领域得到广泛关注。国内外多数研究集中于LDH可控合成工艺的改进完善及LDH的应用探索，但迄今对制备LDH时涉及其组成结构形貌的变化过程，即其形成机理的关注较少，相关机制解释模糊，深入研究其形成过程对于可控制备具有独特形貌和特定组成的LDH及开发更深层次的应用具有至关重要的作用。本文介绍了LDH层板形成机理的3个主要研究方向，即以二价金属氢氧化物的存在为基础、以三价金属氢氧化物的存在为基础和拓扑相变机制，并分别进行了阐述辨析及对比分析，发现LDH层板的形成是一个极其复杂的过程，多种机制往往共同作用，总结认为固液及液液反应在初期成核阶段占据主导地位，各自作用程度及不同层板构筑机制产生的主导作用易受到外界环境因素影响，而更为普遍的LDH形成机制解释需要归纳总结更多LDH层板构筑的区别和规律，宏观和微观上探索形成过程的内在机理及科学本质，以期为LDH开发拓展提供理论基础。

关键词: 层状双金属氢氧化物, 形成机理, 氢氧化物, 拓扑相变, 化学反应

Abstract: Layered double hydroxide (LDH) are a kind of promising special multifunctional layered materials, which have the excellent regulatable capability, perfect environmental compatibility and remarkable efficiency, so they have been studied extensively in environmental protection, catalysis, energy storage, transducer and other fields. Most researches are conducted on the improvement of tailored synthesis methods and application of LDH, whereas the research on the transformation of LDH (composition, structure and morphology)is rare, especially on the general formation mechanism of LDH. The controllable preparation and in-depth applications of LDH with unique morphology and specific composition are highly demanded. An overview and comparison are presented on the interpretations of primary LDH laminate formation mechanisms which are the existence of divalent metal hydroxide, the existence of trivalent metal hydroxides and the direct topological phase transition mechanism. The solid-liquid and liquid-liquid reactions are thought to play a dominant role in the initial nucleation stage, while the multiple mechanisms, the various influences and the mastery reaction are easily affected by the external conditions. To obtain a more universal mechanistic insight on LDH formation and provide a theoretical basis for the prospective development of LDH, a general formation mechanism need to be clarified, which requires explanations from the conclusive building rules and difference of LDH laminate as well as the internal mechanism and scientific nature of the formation process in macro and micro perspectives.

Key words: layered double hydroxide(LDH), formation mechanism, hydroxide, topological mechanism, chemical reaction

中图分类号:

TQ13
O611.64

张胜寒, 陈玉强, 姜亚青, 孙晨皓. 层状双金属氢氧化物形成机理的研究现状[J]. 化工进展, 2018, 37(01): 128-139.

ZHANG Shenghan, CHEN Yuqiang, JIANG Yaqing, SUN Chenhao. Research progress of layered double hydroxide formation mechanisms[J]. Chemical Industry and Engineering Progress, 2018, 37(01): 128-139.

参考文献

[1] 孙金陆,甄卫军,李进. LDHs材料的结构、性质及其应用研究进展[J]. 化工进展,2013,32(3):610-616. SUN Jinlu,ZHEN Weijun,LI Jin. Structure,properties and applications of LDHs[J]. Chemical Industry and Engineering Progress,2013,32(3):610-616.
[2] SAJID M,BASHEER C. Layered double hydroxides:emerging sorbent materials for analytical extractions[J]. Trac Trends in Analytical Chemistry,2016,75:174-182.
[3] TIAN R,LIANG R,WEI M,et al. Applications of layered double hydroxide materials:recent advances and perspective[M]//50 Years of Structure and Bonding-The Anniversary Volume,2016.
[4] 王瑞瑞,赵有璟,邵明飞,等. 层状双金属氢氧化物用于催化水氧化的研究进展[J]. 化工学报,2016,67(1):54-72. WANG Ruirui,ZHAO Youjing,SHAO Mingfei,et al. Recent progresses in water oxidation over layered double hydroxide catalysts[J]. CIESC Journal,2016,67(1):54-72.
[5] 陈艳,王丽秋,王晨晔,等. 以钢渣为原料合成层状双氢氧化物及其结构表征[J]. 化工学报,2015,66(12):5149-5156. CHEN Yan,WANG Liqiu,WANG Chenye,et al. Synthesis and structural characterization of layered double hydroxide using steel slag as raw material[J]. CIESC Journal,2015,66(12):5149-5156.
[6] 谢非,李静,晋冠平. 二氧化铈/钙铝水滑石/活性炭的制备及环境应用[J]. 化工进展,2016,35(1):182-188. XIE Fei,LI Jing,JIN Guanping. Preparation of CeO₂/CaAl-LDHs/AC and its environmental applications[J]. Chemical Industry and Engineering Progress,2016,35(1):182-188.
[7] LIANG X,ZANG Y,XU Y,et al. Sorption of metal cations on layered double hydroxides[J]. Colloids & Surfaces A:Physicochemical & Engineering Aspects,2013,433(35):122-131.
[8] MORIMOTO K,ANRAKU S,HOSHINO J,et al. Surface complexation reactions of inorganic anions on hydrotalcite-like compounds[J]. Journal of Colloid & Interface Science,2012,384(1):99-104.
[9] 唐朝春,陈惠民,刘名,等. ZnAl和MgAl水滑石吸附废水中磷的研究进展[J]. 化工进展,2015,34(1):245-251. TANG Chaochun,CHEN Huimin,LIU Ming,et al. Advances in adsorption of phosphate in wastewater by ZnAl and MgAl hydrotalcite[J]. Chemical Industry and Engineering Progress,2015,34(1):245-251.
[10] 刘儒平,孔祥贵,岳钊,等. 水滑石纳米材料特性及其在电化学生物传感器方面的应用[J]. 化工进展,2013,32(11):2661-2667. LIU Ruping,KONG Xianggui,YUE Zhao,et al. Properties and application of layered double hydroxides for electrochemical biosensors[J]. Chemical Industry and Engineering Progress,2013,32(11):2661-2667.
[11] WANG X,LIN Y,SU Y,et al. Design and synthesis of ternary-component layered double hydroxides for high-performance supercapacitors:understanding the role of trivalent metal ions[J]. Electrochimica Acta,2017,225:263-271.
[12] MCLAUGHLIN W J,WHITE J L,HEM S L. Influence of heterocoagulation on the formation of hydrotalcite in mixed suspensions of magnesium hydroxide and aluminum hydroxycarbonate[J]. Journal of Colloid & Interface Science,1994,165:41-52.
[13] ZENG S,XU X,WANG S,et al. Sand flower layered double hydroxides synthesized by co-precipitation for CO₂ capture:morphology evolution mechanism,agitation effect and stability[J]. Materials Chemistry & Physics,2013,140(1):159-167.
[14] SALIBA D,ALGHOUL M. Stability and particle size control of self-assembled cadmium-aluminum layered double hydroxide[J]. Crystengcomm,2016,18:8445-8453.
[15] CHANG Z,WU C,SONG S,et al. Synthesis mechanism study of layered double hydroxides based on nanoseparation[J]. Inorganic Chemistry,2013,52(15):8694-8698.
[16] SOLOVOV V,KOVALENKO V,NIKOLENKO N,et al. Influence of temperature on the characteristics of Ni(Ⅱ),Ti(Ⅳ) layered double hydroxides synthesised by different methods[J]. Eastern-European Journal of Enterprise Technologies,2017,1/6(85):16-22.
[17] 任庆利,陈维,罗强. 液相法合成针状镁铝水滑石纳米晶的研究[J]. 无机材料学报,2004,19(5):977-984. REN Qingli,CHEN Wei,LUO Qiang. Preparation of aeicular nanocrystalline Mg, Al-hydrotalcite by liquid method[J]. J. Inorg. Mater.,2004,19(5):976-984.
[18] 黄炎,曾虹燕,王亚举,等. 尿素法合成镁铁水滑石的制备机理[J]. 硅酸盐学报,2011,39(2):365-370. HUANG Yan,ZENG Hongyan,WANG Yaju,et al. Preparation mechanism of the Mg-Fe hydrotalcite with urea method[J]. Journal of the Chinese Ceramic Society, 2011,39(2):365-370.
[19] GRÉGOIRE B,RUBY C,CARTERET C. Hydrolysis of mixed Ni²⁺-Fe³⁺ and Mg²⁺-Fe³⁺ solutions and mechanism of formation of layered double hydroxides[J]. Dalton Transactions,2013,42(44):15687-15698.
[20] TAN X,FANG M,REN X,et al. Correction to effect of silicate on the formation and stability of Ni-Al LDH at the γ-Al₂O₃ surface[J]. Environmental Science & Technology,2015,49(10):13138-13145.
[21] LEE G,JI Y K,NING Y,et al. Simple preparation method for Mg-Al hydrotalcites as base catalysts[J]. Journal of Molecular Catalysis A:Chemical,2016,423:347-355.
[22] PALLAGI A,ÁGOST T,GÁCSI A,et al. The solubility of Ca(OH)₂,in extremely concentrated NaOH solutions at 25℃[J]. Central European Journal of Chemistry,2012,10(2):332-337.
[23] ELISEEV A A,LUKASHIN A V,VERTEGEL A A,et al. A study of crystallization of Mg-Al double hydroxides[J]. Doklady Chemistry,2002,387(4):339-343.
[24] BOCLAIR J W,BRATERMAN P S. Layered double hydroxide stability. 1. Relative stabilities of layered double hydroxides and their simple counterparts[J]. Chemistry of Materials,1999,11(2):298-302.
[25] OESTREICHER V,FÁBREGAS I,JOBBÁGY M. One-pot epoxide-driven synthesis of M₂Al(OH)₆Cl·1.5H₂O layered double hydroxides:precipitation mechanism and relative stabilities[J]. Journal of Physical Chemistry C,2014,118(51):30274-30281.
[26] 苟国敬. 镁铝层状复合氢氧化物微晶的合成与应用基础研究[D]. 西宁:中国科学院研究生院(青海盐湖研究所),2005. GOU Guojing. Basic research on synthesis and application performance of micro-crystal of Mg-Al layered double hydroxides[D]. Xining:Chinese Academy of Sciences(Qinghai Institute of Salt Lakes),2005.
[27] YANG Y,ZHAO X,ZHU Y,et al. Transformation mechanism of magnesium and aluminum precursor solution into crystallites of layered double hydroxide[J]. Chemistry of Materials,2012,24(1):81-87.
[28] 阴青青. 镍铝类水滑石的转化形成及其催化性能研究[D]. 太原:太原理工大学,2016. YIN Qingqing. Process formation investigation of NiAl-LDHs and its catalytic performances evaluation[D]. Taiyuan:Taiyuan University of Technology,2016.
[29] LIU J,SONG J,XIAO H,et al. Synthesis and thermal properties of ZnAl layered double hydroxide by urea hydrolysis[J]. Powder Technology,2014,253(2):41-45.
[30] CHEN J,SONG Y,SHAN D,et al. Study of the in situ growth mechanism of Mg-Al hydrotalcite conversion film on AZ31 magnesium alloy[J]. Corrosion Science,2012,63(5):148-158.
[31] ZENG R C,LIU Z G,ZHANG F,et al. Corrosion resistance of in-situ Mg-Al hydrotalcite conversion film on AZ31 magnesium alloy by one-step formation[J]. Transactions of Nonferrous Metals Society of China,2015,25(6):1917-1925.
[32] PAIKARAY S,GOMEZ M A,HENDRY M J,et al. Formation mechanism of layered double hydroxides in Mg²⁺-,Al³⁺-,and Fe³⁺-rich aqueous media:implications for neutralization in acid leach ore milling[J]. Applied Clay Science,2014,101:579-590.
[33] HASE H,NISHIUCHI T,SATO T,et al. A novel method for remediation of nickel containing wastewater at neutral conditions[J]. Journal of Hazardous Materials,2017,329:49-56.
[34] XU Y,JIA Z,ZHOU J,et al. CN and heavy metal removal through formation of layered double hydroxides from mixed CN-containing electroplating wastewaters and pickle acid liquor[J]. Chemical Engineering Journal,2013,s 215/216(2):411-417.
[35] XU Y,ZHANG J,LIANG Y,et al. Synchronous cyanide purification with metals removal in the co-treatment of Zn-CN and Ni electroplating wastewaters via the Ni²⁺-assisted precipitation of LDH[J]. Separation & Purification Technology,2015,145:92-97.
[36] IGLESIAS L,WALTHER C,MEDINA F,et al. A comprehensive study on iodine uptake by selected LDH phases via coprecipitation,anionic exchange and reconstruction[J]. Journal of Radioanalytical and Nuclear Chemistry,2016,307(1):111-121.
[37] ZHI L,ZHANG F,LEI X,et al. In situ growth of layered double hydroxide films on anodic aluminum oxide/aluminum and its catalytic feature in aldol condensation of acetone[J]. Chemical Engineering Science,2008,63(16):4055-4062.
[38] 彭家惠,楼宗汉. 钙矾石形成机理的研究[J]. 硅酸盐学报,2000,28(6):511-515. PENG Jiahui,LOU Zonghan. Study on the mechanism of ettringite formation[J]. Journal of The Chinese Ceramic Society,2000,28(6):511-515.
[39] STANIMIROVA T. Cation selectivity during re-crystallization of layered double hydroxides from mixed (Mg,Al)oxides[J]. Bulletin of Mineralogy Petrology & Geochemistry,2007,22(6):295-301.
[40] RADHA A V,KAMATH P V,SHIVAKUMARA C. Mechanism of the anion exchange reactions of the layered double hydroxides (LDHs) of Ca and Mg with Al[J]. Solid State Sciences,2005,7(10):1180-1187.
[41] QIU X,SASAKI K,YU T,et al. Mechanism of boron uptake by hydrocalumite calcined at different temperatures[J]. Journal of Hazardous Materials,2015,287:268-277.
[42] ALMASRI D,MAHMOUD K A,ABDEL-WAHAB A. Two-stage sulfate removal from reject brine in inland desalination with zero-liquid discharge[J]. Desalination,2015,362:52-58.
[43] JONES M R,MACPHEE D E,CHUDEK J A,et al. Studies using ²⁷Al MAS NMR of AFm,and AFt phases and the formation of Friedel's salt[J]. Cement & Concrete Research,2003,33(2):177-182.
[44] MA Jiayu,LI Zhibao,JIANG Yuehua,et al. Synthesis,characterization and formation mechanism of Friedel's salt(FS:3CaO·Al₂O₃·CaCl₂·10H₂O)by the reaction of calcium chloride with sodium aluminate[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed.,2015,30(1):76-83.
[45] WU J S,XIAO Y K,WAN J Y,et al. The growth mechanism of hydrotalcite crystal[J]. Science China:Technological Sciences,2012,55(4):872-878.
[46] ADACHIPAGANO M,FORANO C,BESSE J P. Synthesis of Al-rich hydrotalcite-like compounds by using the urea hydrolysis reaction-control of size and morphology[J]. Journal of Materials Chemistry,2003,13(8):1988-1993.
[47] RAO M M,REDDY B R,JAYALAKSHMI M,et al. Hydrothermal synthesis of Mg-Al hydrotalcites by urea hydrolysis[J]. Materials Research Bulletin,2005,40(2):347-359.
[48] NAGHASH A,ETSELL T H,LU B. Mechanisms involved in the formation and growth of Al-Cu-Ni hydrotalcite-like precipitates using the urea hydrolysis scheme[J]. Journal of Materials Chemistry,2008,18(22):2562-2568.
[49] TAMURA H,CHIBA J,ITO M,et al. Formation of hydrotalcite in aqueous solutions and intercalation of ATP by anion exchange[J]. Journal of Colloid & Interface Science,2006,300(2):648-654.
[50] 马向荣,李红娟,张智芳,等. 十二烷基磺酸根插层Ni²⁺-Fe³⁺/Co²⁺-Ni²⁺-Fe³⁺ LDHs及其结构研究[J]. 应用化工,2011,40(6):1007-1010. MA Xiangrong,LI Hongjuan,ZHANG Zhifang,et al. Preparation and structure of dodecyl sulfonate-pillared Ni²⁺-Fe³⁺/Co²⁺-Ni²⁺-Fe³⁺ LDHs[J]. Applied Chemical Industry,2011,40(6):1007-1010.
[51] HASANNIA S,YADOLLAHI B. Zn-Al LDH nanostructures pillared by Fe substituted Keggin type polyoxometalate:synthesis,characterization and catalytic effect in green oxidation of alcohols[J]. Polyhedron,2015,99:260-265.
[52] 李腾飞,王泽林,许艳旗,等. 多酸插层水滑石复合材料的新进展[J]. 中国科学:化学,2017,47(4):451-464. LI Tengfei,WANG Zelin,XU Yanqi,et al. Recent progress in polyoxometalate-intercalated layered double hydroxides composite materials[J]. Scientia Sinica Chimica,2017,47(4):451-464.
[53] THEISS F L,COUPERTHWAITE S J,AYOKO G A,et al. A review of the removal of anions and oxyanions of the halogen elements from aqueous solution by layered double hydroxides[J]. Journal of Colloid & Interface Science,2014,417:356-368.
[54] STOICA G,CASTELLÓ S I,FIGUEROLA A,et al. Layered double hydroxides as carriers for quantum dots@silica nanospheres[J]. Nanoscale,2012,4(17):5409-5419.
[55] NISHIMURA S,TAKAGAKI A,EBITANI K. ChemInform abstract:characterization,synthesis and catalysis of hydrotalcite-related materials for highly efficient materials transformations[J]. Cheminform,2013,44(40):2026-2042.
[56] KAMEDA T,UMETSU Y. Effect of preparation method on particle properties of carbonate-type magnesium-aluminum layered double hydroxides[J]. Journal of Industrial & Engineering Chemistry,2017,53:105-110.
[57] QU J,HE X,CHEN M,et al. Mechanochemical synthesis of Cu-Al and methyl orange intercalated Cu-Al layered double hydroxides[J]. Materials Chemistry & Physics,2017,191:173-180.
[58] FERENCZ Z,SZABADOS M,VARGA G,et al. Mechanochemical synthesis and intercalation of Ca(Ⅱ)Fe(Ⅲ)-layered double hydroxides[J]. Journal of Solid State Chemistry,2016,233:236-243.
[59] FAHAMI A,BEALL G W. Mechanosynthesis and characterization of hydrotalcite like Mg-Al-SO₄-LDH[J]. Materials Letters,2016,165:192-195.