阴离子对Mg(OH)2晶体生长及形貌的影响机理

doi:10.11949/j.issn.0438-1157.20170416

化工学报 ›› 2017, Vol. 68 ›› Issue (10): 3985-3992.DOI: 10.11949/j.issn.0438-1157.20170416

• 材料化学工程与纳米技术 • 上一篇

阴离子对Mg(OH)₂晶体生长及形貌的影响机理

程沛¹, 李雪^1,2,3, 裴冰野¹, 常睿璇¹, 孙晓君¹, 丁珂¹, 范天博^1,2,3, 刘云义^1,2,3

1 沈阳化工大学化学工程学院, 辽宁沈阳 110142;
2 辽宁省化工应用重点实验室, 辽宁沈阳 110142;
3 辽宁精细化工协同创新中心, 辽宁沈阳 110142

收稿日期:2017-04-16 修回日期:2017-07-06 出版日期:2017-10-05 发布日期:2017-10-05
通讯作者: 李雪,ltmlx@163.com
基金资助:
国家重点基础研究发展计划项目（2014CB744300）；辽宁省自然科学基金项目（L2015020609）；辽宁省创新团队项目（LT2013010）。

Influence mechanism of anions on growth and morphology of Mg(OH)₂ crystal

CHENG Pei¹, LI Xue^1,2,3, PEI Bingye¹, CHANG Ruixuan¹, SUN Xiaojun¹, DING Ke¹, FAN Tianbo^1,2,3, LIU Yunyi^1,2,3

1 College of Chemical Engineering, Shenyang University of Chemical Technology, Shenyang 110142, Liaoning, China;
2 Key Laboratory of Applied Technology for Chemical Engineering Liaoning Province, Shenyang 110142, Liaoning, China;
3 Liaoning Collaborative Innovation Center of Fine Chemical Industry, Shenyang 110142, Liaoning, China

Received:2017-04-16 Revised:2017-07-06 Online:2017-10-05 Published:2017-10-05
Supported by:
supported by the National Basic Research Program of China(2014CB744300), the Natural Science Foundation of Liaoning Province (L2015020609) and the Liaoning Provincial Innovation Team Project (LT2013010).

摘要/Abstract

摘要：

以轻烧粉、氯化铵、硝酸铵、乙酸铵、硫酸铵为原料，氨气为沉淀剂，采用氨循环法制备氢氧化镁晶体，并通过扫描电镜（SEM）、X射线衍射（XRD）对其进行表征分析。采用Materials Studio分子模拟软件中的CASTEP模块，计算了Cl^-、NO₃^-、CH₃COO^-对氢氧化镁晶体（001）、（101）晶面生长的影响。结果表明，采用不同的镁盐得到不同形貌的氢氧化镁晶体阴离子电负性越大，对晶体形貌影响越小；Mg（OH）₂晶体的（001）、（101）晶面能量与布居数分析表明，Cl^-、NO₃^-、CH₃COO^-使晶体的（001）、（101）面的表面能增大、Fermi能级减小，阴离子与（001）、（101）晶面之间形成新的具有微弱共价性的离子键，影响晶体晶面的生长。理论计算较好地解释了不同形貌的氢氧化镁晶体的形成原因。

关键词: 轻烧粉, 电负性, 分子模拟, 布居数, 机理

Abstract:

The magnesium hydroxide crystals were prepared by ammonia circulation method,using light burning powder,ammonium chloride,ammonium nitrate,ammonium acetate and ammonium sulfate as raw materials and ammonia gas as precipitant.X-ray diffraction (XRD) and scanning electron microscopy (SEM) have been employed to characterize these products.The effects of Cl^-,NO₃^- and CH₃COO^- on the growth of (001) and (101) crystal planes of magnesium hydroxide crystals were calculated by the CASTEP module in the Materials Studio molecular simulation software.The results showed that magnesium hydroxide crystals with different morphologies were obtained by different magnesium salts.The larger the anionic electronegativity was,the smaller the effect on the crystal morphology.The (001) and (101) crystal face energy and population analysis of Mg (OH)₂ crystals showed that the surface energy increased and Fermi energy decreased of (001) and (101) planes of the crystals with Cl^-,NO₃^- and CH₃COO^-.New ionic bond with weak covalency was formed between anion and the (001) and (101) planes which affected the growth of the crystal plane.The theoretical calculations explained the formation of magnesium hydroxide crystals with different morphologies.

Key words: light burning powder, electronegativity, molecular simulation, population, mechanism

中图分类号:

TQ132.2

程沛, 李雪, 裴冰野, 常睿璇, 孙晓君, 丁珂, 范天博, 刘云义. 阴离子对Mg(OH)₂晶体生长及形貌的影响机理[J]. 化工学报, 2017, 68(10): 3985-3992.

CHENG Pei, LI Xue, PEI Bingye, CHANG Ruixuan, SUN Xiaojun, DING Ke, FAN Tianbo, LIU Yunyi. Influence mechanism of anions on growth and morphology of Mg(OH)₂ crystal[J]. CIESC Journal, 2017, 68(10): 3985-3992.

参考文献 36

[1]	黄涛, 乔建江, 张颐年, 等. 氢氧化镁阻燃剂的制备及其应用[J]. 华东理工大学学报, 2015, 41(1):60-65. HUANG T, QIAO J J, ZHANG Y N, et al. Preparation and application of magnesium hydroxide as flame retardant[J]. Journal of East China University of Science and Technology 2015, 41(1):60-65.
[2]	向兰, 王靖. 水热法制备纳米分散颗粒和晶须材料进展[J]. 化工学报, 2014, 65(7):2638-2644. XIANG L, WANG J. Progress in hydrothermal formation of dispersive nanoparticles and whiskers[J]. CIESC Journal, 2014, 65(7):2638-2644.
[3]	李志强, 吴庆流, 向兰, 等. 常温合成条件对两步法制备氢氧化镁阻燃剂中试研究的影响[J]. 化工学报, 2005, 56(6):1106-1111. LI Z Q, WU Q L, XIANG L, et al. Influence of synthesis condition on magnesium hydroxdie properties by two-step reaction on pilot scale[J]. Journal of Chemical Industry and Engineering(China), 2005, 56(6):1106-1111.
[4]	董国义, 葛世艳, 韦志仁, 等. 水热法α-Al2O3自发结晶和形态控制[J]. 人工晶体学报, 2004, 33(3):380-383. DONG G Y, GE S Y, WEI Z R, et al. Morphological forms control of α-Al2O3 crystal spontaneously synthesized by hydrothermal method[J]. Journal of Synthetic Crystals, 2004, 33(3):380-383.
[5]	SAIN M, PARK S H, SUHARA F, et al. Flame retardant and mechanical properties of natural fibre-PP composites containing magnesium hydroxide[J]. Polymer Degradation and Stability, 2004, 83(2):363-367.
[6]	宋雪雪, 李丽娟, 时东, 等. 硫酸镁-氨气法生产氢氧化镁[J]. 盐湖研究, 2013, 21(4):42-48. SONG X X, LI L J, SHI D, et al. Research of synthesizing magnesium hydroxide with magnesium sulfate and NH3[J]. Salt Lake Research, 2013, 21(4):42-48.
[7]	BRINDLEY G W, CHIH C K. Stuctural and IR relations among brucite-like divalent metal hydroxide[J]. Physies and Chemistry of Minerals. 1984, 10(4):187-191.
[8]	顾志宏. 无卤阻燃剂氢氧化镁在EPDM中的应用研究[J]. 世界橡胶工业, 2008, 35(11):1-4. GU Z H. Magnesium hydroxide as halogen-free flame retardant for EPDM applications[J]. World Rubber Industry, 2008, 35(11):1-4.
[9]	吴湘锋. 阻燃型氢氧化镁的制备及其在聚丙烯中应用技术研究[D]. 太原:中北大学, 2008. WU X F. Preparation of magnesium hydroxide as fire-retardant and application in polypropylene[D]. Taiyuan:North University of China, 2008.
[10]	胡含, 谢佳阳, 李雪, 等. 氨气法制备多形貌氢氧化镁及对氧化镁活性的影响[J]. 无机盐工业, 2014, 46(9):29-32. HU H, XIE J Y, LI X, et al. Preparation of Mg(OH)2 with different morphology by ammonia methed and research of their influences on MgO activity[J]. Journal of Inorganic Salt Industry, 2014, 46(9):29-32.
[11]	李雪, 程沛, 侯睿, 等. 轻烧粉氨气法制备氢氧化镁阻燃剂的研究[J]. 无机盐工业, 2016, 48(11):21-24. LI X, CHENG P, HOU R, et al. Preparation of Mg(OH)2 with caustic calcined magnesia through ammonium circulation[J]. Journal of Inorganic Salt Industry, 2016, 48(11):21-24.
[12]	罗仙平, 王金庆, 董竑君, 等. 纳米氢氧化镁的制备及表征方法研究进展[J]. 盐业与化工, 2016, 45(6):14-19. LUO X P, WANG J Q, DONG H J, et al. Research progress of preparation and characterization of nano-magnesium hydroxide[J]. Salt Industry and Chemical Industry, 2016, 45(6):14-19.
[13]	于文强, 乔建江. 高分散高微细阻燃型氢氧化镁合成工艺的研究[J]. 华东理工大学学报(自然科学版), 2016, 42(4):521-528. YU W Q, QIAO J J. Synthesis of flame retardant magnesium hydroxide with high dispersion and high degree of fineness[J]. Journal of East China University of Science and Technology (Natural Science Edition), 2016, 42(4):521-528.
[14]	魏海平. 氨法制备氢氧化镁研究综述[J]. 化工管理, 2016, 402(5):207. WEI H P. Review of ammonia preparation of magnesium hydroxide[J]. Chemical Management, 2016, 402(5):207.
[15]	王明帆, 马祥伟, 游轻寒, 等. 活性氢氧化镁水热改性制备分散性氢氧化镁[J]. 无机盐工业, 2015, 47(7):29-31. WANG M F, MA X W, YOU Q H, et al. Preparation of dispersible magnesium hydroxide via hydrothermal modification of active magnesium hydroxide[J]. Journal of Inorganic Salt Industry, 2015, 47(7):29-31.
[16]	李三喜, 任晓宇, 王松. 水热改性对氢氧化镁的影响[J]. 沈阳工业大学学报, 2015, 37(4):372-376. LI S X, REN X Y, WANG S. Effect of hydrothermal modification on magnesium hydroxide[J]. Journal of Shenyang University of Technology, 2015, 37(4):372-376.
[17]	李秀红. 片状氢氧化镁晶种的制备研究[J]. 安徽化工, 2011, 37(6):31-35. LI X H. Study on seeds of platelike magnesium hydroxide[J]. Journal of Chemical Industry in Anhui, 2011, 37(6):31-35.
[18]	王小军, 秦亮, 何丹, 等. 2,4,6-三硝基-2,4,6-三氮杂环己酮的晶体形貌预测[J]. 化学研究, 2012, 23(2):17-21. WANG X J, QIN L, HE D, et al. Prediction of crystal morphology of 1-oxo-2,4,6-trinitro-2,4,6-triazacyclohexane[J]. Chinese Journal of Chemical Research, 2012, 23(2):17-21.
[19]	崔文颖, 刘子忠, 蒋亚军, 等. TiO2表面吸附三氟乙酸的密度泛函理论研究[J]. 化学学报, 2012, 70(19):2049-2058. CUI W Y, LIU Z Z, JIANG Y J, et al. Density functional theory study on adsorption of trifluoroacetic acid on TiO2 surface[J]. Acta Chimica Sinica, 2012, 70(19):2049-2058.
[20]	徐昀. 氧原子在Ni (110)和Ni (111)表面吸附的密度泛函理论研究[D]. 沈阳:东北大学, 2008. XU Y. A density functional theory study of oxygen adsorbed on Ni (110) and Ni (111) surfaces[D]. Shenyang:Northeastern University, 2008.
[21]	熊晓玲, 李兴亮, 罗顺忠, 等. 六方WO3晶体形貌模拟及最佳纳米尺度计算研究[J]. 计算机与应用化学, 2013, 30(4):357-360. XIONG X L, LI X L, LUO S Z, et al. Simulation of crystal surface morphologies and calculation of minimum and optimum nano-particles of Hexagonal WO3[J]. Computer & Applied Chemistry, 2013, 30(4):357-360.
[22]	朱树红. 基于CASTEP软件的硼氢化锂解氢机理的研究[J]. 装备制造技术, 2016, 262(10):137-139. ZHU S H. Study on the mechanism of lithium hydride solution based on CASTEP software[J]. Equipment Manufacturing Technology, 2016, 262(10):137-139.
[23]	周永红, 范天博, 刘露萍, 等. 六方片状氢氧化镁的合成及其第一性原理分析[J]. 化工学报, 2016, 67(9):3843-3849. ZHOU Y H, FAN T B, LIU L P, et al. Prearation of hexagonal plates of magnesium hydroxide and mechanism analysis with first principles[J]. CIESC Journal, 2016, 67(9):3843-3849.
[24]	范天博, 王怀士, 张研, 等. 高温体系合成六方片状氢氧化镁晶体生长机理的研究[J]. 人工晶体学报, 2014, 43(9):2276-2280+2285. FAN T B, WANG H S, ZHANG Y, et al. Study on growth mechanism of hexagonal flake magnesium hydroxide crystal synthesized under high temperature systems[J]. Journal of Synthetic Crystals, 2014, 43(9):2276-2280+2285.
[25]	丁绪淮, 谈遒. 工业结晶学[M]. 北京:化学工业出版社, 1985. DING X J, TAN Q. Industrial Crystallography[M]. Beijing:Chemical Industry Press, 1985.
[26]	戴益民, 聂长明. 逐级加合均分法计算基团电负性公式的改进[J]. 南华大学学报(自然科学版), 2007, 21(2):64-67. DAI Y M, NIE C M. Revised formuia for graddual sum even way to caculate group electronegativity[J]. Journal of Nanhua University (Natural Science Edition), 2007, 21(2):64-67.
[27]	ZHANG Y Y, LIU X, XIONG Z H, et al. Compressional behavior of MgCr2O4 spinel from first-principles simulation[J]. Science China (Earth Sciences), 2016, 59(5):989-996.
[28]	SEGALL M D, LINDAN P J D, PROBER M J, et al. First-principles simulation:ideas, illustrations and the CASTEP code[J]. Journal of Physics:Condensed Matter, 2002, 14(11):2717-2744.
[29]	FLORENCE A J, BARDIN J, JOHNSTON B, et al. Structure determination from powder data:mogul and CASTEP[J]. Zeitschrift für Kristallographie Supplements, 2009, 2009(30):215-220.
[30]	PERDEW J P, BURKE K, ERNZERHOF M, et al. Generalized gradient approximation made simple[J]. Phys. Rev. Lett, 1996, 77(18):3865-3868.
[31]	MARLO M, MILMAN V. Density-functional study of bulk and surface properties of titanium nitride using different exchange-correlation functional[J]. Phys. Rev. B, 2000, 62(4):2899.
[32]	田凯, 涂学炎, 戴树珊. 在Rh(111)面上NO+CO反应机理的密度泛函理论研究[J]. 高等学校化学学报, 2008, 29(12):2360-2364. TIAN K, TU X Y, DAI S S. Density functional theory study of NO+CO reaction mechanism on the Rh(111) surface[J]. High School Chemistry Report, 2008, 29(12):2360-2364.
[33]	吴争平, 尹周澜, 陈启元, 等. 氢氧化铝表面性质的CASTEP计算及其晶面叠合分析[J]. 中国有色金属学报, 2009, 19(1):179-188. WU Z P, YIN Z L, CHEN Q Y, et al, CASTEP calculation of surface property of gibbsite and analysis of crystal surface combination[J]. Journal of Nonferrous Metals, 2009, 19(1):179-188.
[34]	WANG G Y, QIU Z B. Crystalline morphology and crystallization kinetics of melt-miscible crystalline/crystalline polymer blends of poly(vinylidene fluoride) and poly(butylene succinate-co-24mol% hexamethylene succinate)[J]. Chinese Journal of Polymer Science, 2014, 32(9):1139-1148.
[35]	贺战文, 康少波. 基于CASTEP软件的TiCx结构构建及性能研究[J]. 武汉轻工大学学报, 2016, 35(4):43-46. HE Z W, KANG S B. Study of structure & properties of the nonstoichiometric of TiCx based on CASTEP software[J]. Journal of Wuhan University of Light Industry, 2016, 35(4):43-46.
[36]	CHEN Q Y, WU Z P, YIN Z L, et al. Bond population analysis on combination of favorable growth unit of Al(OH)3 crystals[J]. Trans. Nonferrous Met. Soc. China, 2006, 16(1):191-197.

阴离子对Mg(OH)₂晶体生长及形貌的影响机理

Influence mechanism of anions on growth and morphology of Mg(OH)₂ crystal

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