制备条件对掺镁羟基磷灰石结构及除氟性能的影响
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摘要
为了提高羟基磷灰石(HAP)滤料的除氟能力,以磷酸、四水硝酸钙和六水硝酸镁为原料,采用化学沉淀法制备一种Mg掺杂羟基磷灰石(Mg-HAP)除氟滤料,研究了制备条件对滤料除氟性能的影响,探究了Mg-HAP滤料的结构与除氟性能之间的关系。结果表明:掺镁量和陈化时间主要影响晶体结构;钙、镁与磷的摩尔比和反应温度主要影响Mg-HAP的纯度;在滤料晶体结构相对保持完整时,滤料的羟基含量越多,滤料的除氟容量越高。在n(Mg)/n(Ca+Mg)为0.10,n(Ca+Mg)/n(P)为1.50,反应温度30℃,搅拌1 h,90℃陈化60 min的优化制备工艺条件下,制备的Mg-HAP滤料样品,Mg在HAP的内部分布均匀;Mg取代羟基磷灰石晶格中的少部分Ca,导致晶面结构发生畸变,晶格缺陷增加,表面吸附能力增强;同时滤料的羟基含量提高,滤料的除氟容量提高。与HAP相比,Mg-HAP除氟容量提高了近4倍。
To improve the defluoridation capacity of hydroxyapatite(HAP), a Mg-doped hydroxyapatite(Mg-HAP) was prepared by a chemical precipitation method using H3 PO4, Ca(NO3)2·4 H2 O and Mg(NO3)2·6 H2 O as raw materials. The effect of preparation condition on defluoridation properties of the Mg-HAP was investigated. The relationship between the structure and the defluoridation properties of the Mg-HAP was analyzed. The results indicate that the content of added Mg(n(Mg)/n(Ca+Mg) and aging time mainly affect the crystal structure of Mg-HAP, and the molar ratio(n(Ca+Mg)/n(P)) and the reaction temperature mainly affect the purity of Mg-HAP. The defluoridation capacity of Mg-HAP with the more hydroxyl is greater. The Mg-HAP sample can be prepared under optimized condition(i.e., n(Mg)/n(Ca+Mg) of 0.10, n(Ca+Mg)/n(P) of 1.50, reaction temperature of 30 ℃, stirring for 1 h, aging at90 ℃ for 60 min). Under the optimized condition, Mg is evenly distributed on the surface of HAP, and the amount of Ca in the lattices of HAP is replaced by Mg, thus leading to the distortion of crystal plane and the increase of lattice defects, and strengthening the surface adsorptive capacity. Also, the defluoridation capacity increases with the increase of hydroxyl content. The defluoridation capacity of Mg-HAP is nearly four times greater than that of HAP.
To improve the defluoridation capacity of hydroxyapatite(HAP), a Mg-doped hydroxyapatite(Mg-HAP) was prepared by a chemical precipitation method using H3 PO4, Ca(NO3)2·4 H2 O and Mg(NO3)2·6 H2 O as raw materials. The effect of preparation condition on defluoridation properties of the Mg-HAP was investigated. The relationship between the structure and the defluoridation properties of the Mg-HAP was analyzed. The results indicate that the content of added Mg(n(Mg)/n(Ca+Mg) and aging time mainly affect the crystal structure of Mg-HAP, and the molar ratio(n(Ca+Mg)/n(P)) and the reaction temperature mainly affect the purity of Mg-HAP. The defluoridation capacity of Mg-HAP with the more hydroxyl is greater. The Mg-HAP sample can be prepared under optimized condition(i.e., n(Mg)/n(Ca+Mg) of 0.10, n(Ca+Mg)/n(P) of 1.50, reaction temperature of 30 ℃, stirring for 1 h, aging at90 ℃ for 60 min). Under the optimized condition, Mg is evenly distributed on the surface of HAP, and the amount of Ca in the lattices of HAP is replaced by Mg, thus leading to the distortion of crystal plane and the increase of lattice defects, and strengthening the surface adsorptive capacity. Also, the defluoridation capacity increases with the increase of hydroxyl content. The defluoridation capacity of Mg-HAP is nearly four times greater than that of HAP.
引文
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[23]BATRA Uma,KAPOOR Seema,SHARMA Sonia.Influence of magnesium ion substitution on structural and thermal behavior of nanodimensional hydroxyapatite[J].J Mater Eng Perform,2013,22:1798?1806.
[24]LUO P,NIEL T G.Preparing hydroxyapatite powders with controlled morphology[J].Biomateriols,1996,17:1959?1964.
[2]BHATNAGAR A,KUMAR E,SILLANPAA M.Fluoride removal from water by adsorption:a review[J].Chem Eng J,2011,171(3):811?840.
[3]NASRUL A,SRI M,RAHMAH L M,et al.The removal of fluoride form water based on applid current and membrane types in electrodialyis[J].J Fluorine Chem,2016,191:97?102.
[4]ABE S,SAWANE T,SEKIGUCHI K,et al.Collection of trace fluoride and hydrofluoric acid from aqueous samples by calcium hydroxyapatite[J].Int J Environ Anal Chem,1982,11(2):87?96.
[5]FENG L,XU W H,LIU T F,et al.Heat regeneration of hydroxyapatite/attapulgite composite beads for defluoridation of drinking water[J].J Hazard Mater,2012,221/222(2):228?235.
[6]HE J Y,ZHANG K S,WU S B,et al.Performance of novel hydroxyapatite nanowires in treatment of fluoride contaminated water[J].J Hazard Mater,2016,303(16):119?130.
[7]CHEN L,ZHANG K S,HE J Y,et al.Enhanced fluoride removal from water by sulfate-doped hydroxyapatite hierarchical hollow microspheres[J].Chem Eng J,2016,285:616-624.
[8]HE J,CHEN K,CAI X,et al.A biocompatible and novelly-defined Al-HAP adsorption membrane for highly effective removal of fluoride from drinking water[J].J Colloid Interface Sci,2016,490:97?107.
[9]GONG L Y,FENG L.Preparation and defluorination mechanism of a novel copolymerized hydroxyapatite-aluminium chloride material[J].RSC Adv,2015,5(115):95334?95343.
[10]赵鑫荣,刘佳琪,洪帆,等.铝神经毒性对学习记忆功能的影响[J].解剖学杂志,2018,41(5):590?592.ZHAO Xinrong,LIU Jiaqi,HONG Fan,et al.Chin J Anatomy(in Chinese),2018,41(5):590?592.
[11]PERCIVAL Mark.Bone health and osteoporosis[J].Appl Nutritional Sci Rep.1999,5:1-5.
[12]ANDRéS Nancy C,SIEBEN Juan M,BALDINI Mónica,et al.Electroactive Mg2+-hydroxyapatite nanostructured networks against drug-resistant bone infection strains[J].ACS Appl Mater Interfaces,2018,10(23):19534?19544.
[13]ANDRéS Nancy C,D’ELíA Noelia L,RUSO Juan M,et al.Manipulation of Mg2+-Ca2+switch on the development of bone mimetic hydroxyapatite[J].ACS Appl Mater Interfaces,2017,9(18):15698?15710.
[14]MONTOYA-CISNEROS K L,RENDóN-ANGELES J C,MATAMOROS-VELOZA Z,et al.Low-temperature densification of Mg-doped hydroxyapatite fine powdersunder hydrothermal hot processing conditions[J].Ceram Int,2017,43:11907?11919.
[15]LIGA S,KRISTINE S A,NATALIJA B,et al.Characterization of Mg-substituted hydroxyapatite synthesized by wet chemical method[J].Ceram Int,2014,40:3261-3267.
[16]贾理男,梁成浩,黄乃宝,等.镁基羟基磷灰石/微弧氧化层制备的研究进展[J].表面技术,2013,42(1):109?112.JIA Linan,LIANG Chenghao,HUANG Naibao,et al.Surf Technol(in Chinese),2013,42(1):109?112.
[17]马晓雨,刘永佳,朱邦尚,等.镁掺杂纳米羟基磷灰石的制备及其在载药方面的应用[J].无机化学学报,2018,34(5):917?924.MA Xiaoyu,LIU Yongjia,ZHU Bangshang,et al.Chin Inorg Chem(in Chinese),2018,34(5):917?924.
[18]李星逸,马野,袁世丹.多孔含镁羟基磷灰石的烧结行为及其组织结构[J].中国体视学与图像分析,2015,20(4):392?399.LI Xingyi,MA Ye,YUAN Shidan.Chin J Stereol Image Anal(in Chinese),2015,20(4):392?399.
[19]OMER K,SERHAT K,NIYAZI B,et al.Characterization of Mg-containing hydroxyapatites synthesized by combustion method[J].Phys B:Condens Matter,2018,537:63?67.
[20]MONDAL P,MEHTA D,SAHARAN V K,et al.Continuous column studies for water defluoridation using synthesized magnesiumincorporated hydroxyapatite pellets:Experimental and modeling studies[J].Environ Process,2018,5:261?285.
[21]CHEN Z,FENG L,MAO L,et al.Effect of cation doping on the structure of hydroxyapatite and the mechanism of defluoridation[J].Ceram Int,2018,44:6002?6009.
[22]李志宏,黄姝杰,武继民,等.含镁羟基磷灰石的制备与性能研究[J].功能材料,2010,41(4):700?703.LI Zhihong,HUANG Shujie,WU Jimin,et al.J Funct Mater(in Chinese),2010,41(4):700?703.
[23]BATRA Uma,KAPOOR Seema,SHARMA Sonia.Influence of magnesium ion substitution on structural and thermal behavior of nanodimensional hydroxyapatite[J].J Mater Eng Perform,2013,22:1798?1806.
[24]LUO P,NIEL T G.Preparing hydroxyapatite powders with controlled morphology[J].Biomateriols,1996,17:1959?1964.