硼酸盐热力学基元贡献模型及在MgBO2(OH)纳米晶须水热合成过程分析中应用

doi:10.3969/j.issn.0438-1157.2013.02.007

化工学报 ›› 2013, Vol. 64 ›› Issue (2): 443-451.DOI: 10.3969/j.issn.0438-1157.2013.02.007

硼酸盐热力学基元贡献模型及在MgBO₂(OH)纳米晶须水热合成过程分析中应用

朱万诚^1,2,3, 张学一¹, 张强¹, 向兰¹, 朱慎林^1,3

1. 清华大学化学工程系,北京 100084;
2. 曲阜师范大学化学工程系,山东曲阜 273165;
3. 化学工程联合国家重点实验室(清华大学),北京 100084

收稿日期:2012-07-31 修回日期:2012-10-20 出版日期:2013-02-05 发布日期:2013-02-05
通讯作者: 朱万诚,向兰
作者简介:朱万诚(1973—),男,博士,副教授。
基金资助:
国家自然科学基金项目(21276141);化学工程联合国家重点实验室开放课题项目(SKL-ChE-09A02)。

Subunit contribution model for thermodynamic properties of borates and its application in hydrothermal synthesis of MgBO₂(OH) nanowhiskers

ZHU Wancheng^1,2,3, ZHANG Xueyi¹, ZHANG Qiang¹, XIANG Lan¹, ZHU Shenlin^1,3

1. Department of Chemical Engineering, Tsinghua University, Beijing 100084, China;
2. Department of Chemical Engineering, Qufu Normal University, Qufu 273165, Shandong, China;
3. State Key Laboratory of Chemical Engineering(Tsinghua University), Beijing 100084, China

Received:2012-07-31 Revised:2012-10-20 Online:2013-02-05 Published:2013-02-05
Supported by:
supported by the National Natural Science Foundation of China(21276141) and the State Key Laboratory of Chemical Engineering(SKL-ChE-09A02).

摘要/Abstract

摘要： 以MgCl₂·6H₂O、H₃BO₃、NaOH为原料,控制摩尔比Mg:B:Na=2:3:4,经室温共沉淀及水热转化(220～240℃,6.0～30.0 h)制得了单斜相MgBO₂(OH)纳米晶须。借鉴机械混合模型、基团贡献法思想,根据质量守恒原则将硼酸镁盐按照复盐分子式进行基元拆分,通过引入校正因子k,利用复盐基元的基础热力学数据拟合建立了Δ_fH_m及Δ_fG_m等硼酸盐热力学基础数据估算的基元贡献模型,估算了共沉淀产物Mg₇B₄O₁₃·7H₂O及水热产物MgBO₂(OH)不同温度下的Δ_fH_m、Δ_fG_m热力学数据,得到了25～100℃下共沉淀反应及25～250℃下水热转化的Δ_rH_m、Δ_rG_m。结果显示,共沉淀反应在室温条件下可自发进行,水热转化须借助一定温度条件方能自发实现,且反应趋势随水热温度升高时间延长而增大。该热力学基元贡献模型有望为其他结构复杂复盐化合物纳米结构的湿化学法控制合成分析及预测提供借鉴。

关键词: 热力学性质, 硼酸盐, 基元贡献模型, 水热, 纳米晶须

Abstract: Pure monoclinic MgBO₂(OH) nanowhiskers were synthesized by room temperature co-precipitation followed by hydrothermal treatment at 220—240℃ for 6.0—30.0 h, using MgCl₂·6H₂O, H₃BO₃, and NaOH as raw materials with molar ratio of Mg:B:Na=2:3:4.Enlightened by mechanical mixture model and group contribution method, a novel subunit contribution model for the assessment of thermodynamic properties such as Δ_fH_m and Δ_fG_m of borates was developed, by introducing correction factor k and reasonably decomposing the complex double salt metal borates into constitutional subunits according to mass conservation.The as-developed model was utilized to assess Δ_fH_m and Δ_fG_m at various temperatures for precipitate Mg₇B₄O₁₃·7H₂O and hydrothermal product MgBO₂(OH), based on which the values of Δ_rH_m and Δ_rG_m of the co-precipitation of Mg₇B₄O₁₃·7H₂O and hydrothermal conversion to MgBO₂(OH) were obtained.The results show that, the room temperature co-precipitation can occur spontaneously whereas the hydrothermal conversion can only be performed spontaneously at high temperature. The feasibility for the co-precipitation as well as the hydrothermal conversion turns to be higher with the increase in the temperature and time.The subunit contribution model is beneficial for the analysis and prediction of controllable synthesis of other complex double salt nanostructures via the soft-chemistry based method.

Key words: thermodynamic properties, borates, subunit contribution model, hydrothermal, nanowhiskers

中图分类号:

朱万诚, 张学一, 张强, 向兰, 朱慎林. 硼酸盐热力学基元贡献模型及在MgBO₂(OH)纳米晶须水热合成过程分析中应用[J]. 化工学报, 2013, 64(2): 443-451.

ZHU Wancheng, ZHANG Xueyi, ZHANG Qiang, XIANG Lan, ZHU Shenlin. Subunit contribution model for thermodynamic properties of borates and its application in hydrothermal synthesis of MgBO₂(OH) nanowhiskers[J]. CIESC Journal, 2013, 64(2): 443-451.

参考文献 26

[1]	Wang W G, Matsugi K, Fukushima H, Sasaki G.Interfacial reaction in AZ91D magnesium alloy matrix composite reinforced with aluminum borate whisker[J].Materials Transaction, 2007, 48(7):1948-1954
[2]	Duan Yu(段玉), Lu Guimin(路贵民), Song Xingfu(宋兴福), Sun Shuying(孙淑英), Yu Jianguo(于建国).Preparation and growth mechanism of magnesium borate whiskers with high aspect ratio[J].Journal of Inorganic Materials(无机材料学报), 2011, 26(4):364-368
[3]	Li Y, Fan Z, Lu J G, Chang R P H.Synthesis of magnesium borate(Mg2B2O5)nanowires by chemical vapor deposition method[J].Chem.Mater., 2004, 16(13):2512-2514
[4]	Tao X Y, Li X D.Catalyst-free synthesis, structural, and mechanical characterization of twinned Mg2B2O5 nanowires[J].Nano Lett., 2008, 8(2):505-510
[5]	Jiang Jiwei(江继伟), Wang Lei(汪雷), Yang Qing(杨青), Yang Deren(杨德仁).Synthesis of magnesium borate nanorods by sol-gel process[J].Journal of Inorganic Materials(无机材料学报), 2006, 21(4):833-837
[6]	Xu B S, Li T B, Zhang Y, Zhang Z X, Liu X G, Zhao J F.New synthetic route and characterization of magnesium borate nanorods[J].Cryst.Growth & Des., 2008, 8(4):1218-1222
[7]	Zhu W C, Zhang Q, Xiang L, Zhu S.Repair the pores and preserve the morphology:formation of high crystallinity 1D nanostructures via the thermal conversion route[J].Cryst.Growth & Des., 2011, 11(3):709-718
[8]	Chen S H, Jin P P, Schumacher G, Wanderka N. Microstructure and interface characterization of a cast Mg2B2O5 whisker reinforced AZ91D magnesium alloy composite[J].Compos.Sci.Technol., 2010, 70(1):123-129
[9]	Zhu W C, Xiang L, He T B, Zhu S.Hydrothermal synthesis and characterization of magnesium borate hydroxide nanowhiskers[J].Chem.Lett., 2006, 35(10):1158-1159
[10]	Gao Shiyang(高世扬), Song Pengsheng(宋彭生), Xia Shuping(夏树屏), Zheng Mianping(郑绵平).Salt Lake Chemistry:Novel Boron Lithium Salt Lake(盐湖化学:新类型硼锂盐湖)[M].Beijing:Science Press, 2007:149-210
[11]	Li J, Gao S, Xia S, Li B, Hu R.Thermochemistry of hydrated calcium borates[J].J.Chem.Thermodynamics, 1997, 29(10):1071-1075
[12]	Li J, Gao S, Xia S, Li B.Thermochemistry of hydrated magnesium borates[J].J.Chem.Thermodynamics, 1997, 29(4):491-497
[13]	Li J, Li B, Gao S.Thermochemistry of hydrated lithium borates[J].J.Chem.Thermodynamics, 1998, 30(6):681-688
[14]	Li J, Li B, Gao S.Thermochemistry of hydrated potassium and sodium borates[J].J.Chem.Thermodynamics, 1998, 30(4):425-430
[15]	Wang J, Zhu L, Wang B, Xia S.Thermochemistry of hydrated ammonium borates[J].Thermochimica Acta, 2005, 425(1/2):23-26
[16]	Liu Z H, Hu M C.New synthetic method and thermochemistry of szaibelyite[J].Thermochimica Acta, 2004, 411(1):27-29
[17]	Zhu W C, Zhu S L, Xiang L.Successive effect of rolling up, oriented attachment and Ostwald ripening on the hydrothermal formation of szaibelyite MgBO2(OH)nanowhiskers[J].Cryst. Eng. Comm.,2009, 11:1910-1919
[18]	Zhu W C, Xiang L, Zhang X Y, Zhu S L.Influence of process parameters on hydrothermal formation of magnesium borate hydroxide nanowhiskers[J].Mater. Res. Innov., 2007, 11(4):188-192
[19]	Wen Huanfei(温焕飞), Tang Jun(唐军), Chai Penglan(柴鹏兰), Liu Jun(刘俊).High stability of silver substrate based on Ostwald ripening self-assembly process[J].CIESC Journal(化工学报), 2012, 63(7):2298-2302
[20]	Rama Kumar A, Alexandra N, Hillary T B, William H C.Thermochemistry and aqueous solubilities of hydrotalcite-like solids[J].Science, 2002, 296(5568):721-723
[21]	Mostafa A T M G, Eakman J M, Yarbro S L.Prediction of standard heats and Gibbs free energies formation of solid inorganic salts from group contributions[J].Ind. Eng. Chem.Res., 1995, 34(12):4577-4582
[22]	Li J, Li B, Gao S.Calculation of thermodynamic properties of hydrated borates by group contribution method[J].Phys.Chem.Minerals, 2000, 27(5):342-346
[23]	Dean J A.Lange's Handbook of Chemistry(15th ed)(兰氏化学手册)[M].Wei Junfa(魏俊发),trans.2nd ed.Beijing:Science Press, 2003:6.86-6.101
[24]	Liu Z H, Hu M C, Gao S Y.Studies on synthesis, characterization and thermochemistry of Mg2[B2O4(OH)2]·H2O[J].J.Therm.Anal.Cal., 2004, 75(1):73-78
[25]	Zhu Wancheng(朱万诚).Study on controllable synthesis and mechanism of one-dimensional magnesium borates nanomaterials.Beijing:Tsinghua University, 2008:197-200
[26]	Yang Xianwan(杨显万), He Aiping(何蔼平), Yuan Baozhou(袁宝州).Handbook of Thermodynamic Data Calculation of High Temperature Aqueous Solution(高温水溶液热力学数据计算手册)[M].Beijing:Metallurgical Industry Press, 1983:53-344

硼酸盐热力学基元贡献模型及在MgBO₂(OH)纳米晶须水热合成过程分析中应用

Subunit contribution model for thermodynamic properties of borates and its application in hydrothermal synthesis of MgBO₂(OH) nanowhiskers

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 26

相关文章 15

编辑推荐

Metrics

本文评价

[1]	姚晓宇, 沈俊, 李健, 李振兴, 康慧芳, 唐博, 董学强, 公茂琼. 流体气液临界参数测量方法研究进展[J]. 化工学报, 2023, 74(5): 1847-1861.
[2]	陈科, 杜理, 曾英, 任思颖, 于旭东. 四元体系LiCl+MgCl₂+CaCl₂+H₂O 323.2 K相平衡研究及计算[J]. 化工学报, 2023, 74(5): 1896-1903.
[3]	毛元敬, 杨智, 莫松平, 郭浩, 陈颖, 罗向龙, 陈健勇, 梁颖宗. C₆~C₁₀烷醇的SAFT-VR Mie状态方程参数回归及其热物性研究[J]. 化工学报, 2023, 74(3): 1033-1041.
[4]	程文婷, 李杰, 徐丽, 程芳琴, 刘国际. AlCl₃·6H₂O在FeCl₃、CaCl₂、KCl及KCl–FeCl₃溶液中溶解度的实验及预测[J]. 化工学报, 2023, 74(2): 642-652.
[5]	杨松涛, 李东洋, 牛玉清, 李鑫钢, 康绍辉, 李洪, 叶开凯, 周志全, 高鑫. 氟化物势能函数和热力学性质的分子模拟研究进展[J]. 化工学报, 2022, 73(9): 3828-3840.
[6]	魏琳, 郭剑, 廖梓豪, Dafalla Ahmed Mohmed, 蒋方明. 空气流量对空冷燃料电池电堆性能的影响研究[J]. 化工学报, 2022, 73(7): 3222-3231.
[7]	乃学瑛, 吴鹏, 程远, 肖剑飞, 刘鑫, 董亚萍. 水热生长碱式硫酸镁纳米线结晶动力学研究[J]. 化工学报, 2022, 73(7): 3038-3044.
[8]	孙哲, 金华强, 李康, 顾江萍, 黄跃进, 沈希. 基于知识数据化表达的制冷空调系统故障诊断方法[J]. 化工学报, 2022, 73(7): 3131-3144.
[9]	赵娟, 吴梦成, 雷惊雷, 李凌杰. 一步水热法制备电解水析氧反应Ni₃S₂@Mo₂S₃高效催化剂[J]. 化工学报, 2022, 73(4): 1575-1584.
[10]	任嘉辉, 刘豫, 刘朝, 刘浪, 李莹. 基于分子指纹和拓扑指数的工质临界温度理论预测[J]. 化工学报, 2022, 73(4): 1493-1500.
[11]	孙铭泽, 马宁, 李浩然, 姜海峰, 洪文鹏, 牛晓娟. 中低温超临界CO₂及其混合工质布雷顿循环热力学分析[J]. 化工学报, 2022, 73(3): 1379-1388.
[12]	王燕杉, 朱小超, 宋英今, 李易航. 草屑厌氧消化预处理耦合水热炭化研究[J]. 化工学报, 2022, 73(2): 904-913.
[13]	居涛, 李国辉, 耿凤霞. 一步法合成二维Ti₃C₂及其电化学性能研究[J]. 化工学报, 2022, 73(2): 951-959.
[14]	李怀旭, 孙晓岩, 陶少辉, 夏力, 项曙光. 基于分子热力学性质和密度峰聚类的脱硫汽油集总[J]. 化工学报, 2022, 73(12): 5449-5460.
[15]	高腾飞, 李国选, 雷志刚. 从催化裂化柴油中分离联苯的溶剂筛选：实验和计算热力学[J]. 化工学报, 2022, 73(12): 5314-5323.