Nanomineral-Aqueous Solution Interfacial Processes
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摘要: 在地球环境中普遍存在的纳米矿物-水溶液界面对许多基本的地球化学过程都至关重要,因而是纳米地球化学的前沿核心研究领域.简要介绍了纳米矿物-水溶液界面领域的基本概念和近期研究进展.举例描述了纳米矿物团聚、吸附、溶解和化学反应等几个相互关联的主要过程,具体阐述了纳米矿物自身特征(如组成、结构、尺寸、形貌、表面保护剂等)以及环境介质条件(如pH、离子强度、化学反应物质、天然有机质浓度和组成、微生物、光辐射等)对纳米矿物-水溶液界面过程的影响规律和微观机制.针对本领域发展面临的机遇和挑战,为未来的研究方向提出了一些设想和建议.Abstract: Nanomineral-aqueous solution interface is ubiquitous in the earth environment, and is of critical importance to many fundamental geochemical processes. The study on nanomineral-aqueons interfaces is therefore at the forefront of nanogeochemistry. In this paper, it briefly introduces the basic concepts and recent research progresses in the field of nanomineral-aqueons interfaces, and specifically illustrates major interfacial processes including aggregation, adsorption, dissolution and chemical reaction of nanominerals. The effects and microscopic mechanisms of nanomineral characteristics (such as composition, structure, size, morphology, surface protection layer, etc.) and environmental media conditions (including pH, ionic strength, chemical reaction substances, NOM concentration and composition, microorganism, light radiation, etc.) on the interfacial processes are discussed in detail. In view of the opportunities and challenges presented in this field, some suggestions for future research directions are put forward.
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Key words:
- nanogeochemisty /
- mineral-aqueous solution interface /
- nanomineral /
- sorption /
- dissolution /
- aggregation
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图 1 自然界存在的纳米矿物的透射电镜照片
a.卡林型金矿床含砷黄铁矿中浸染状分布的金纳米颗粒(Reich et al., 2005);b.洛川黄土中的纳米棒状方解石(陈天虎等, 2005);c.位于Miles Crossing河床中的6-线水铁矿(Hochella et al., 2005);d.Murchison陨石中平均粒径3 nm的纳米金刚石(Dai et al., 2002)
Fig. 1. TEM images of naturally occurring nanominerals and mineral nanoparticles
图 2 多种铁氧化物和羟基氧化物的吉布斯自由能随比表面积(或粒径)的变化
Fig. 2. Gibbs free energy of various iron oxides and oxyhydroxides as a function of specific surface area (or particle size)
图 4 柠檬酸盐保护的纳米银的附着系数随不同离子浓度的变化(pH=7.0)
据Huynh and Chen(2011).a.NaCl;b.CaCl2和MgCl2
Fig. 4. Attachment efficiencies of citrate-coated AgNPs as functions of NaCl (a) and CaCl2 and MgCl2 (b) concentrations at pH=7.0
图 6 CeO2纳米粒子在过滤和未过滤的莱茵河、默兹河水样中沉降12 d后的平均剩余浓度
Fig. 6. Residual concentrations of CeO2 nanoparticles after 12 d of settling in filtered and unfiltered river water, average of concentration in Rhine and Meuse Rivers
图 7 Ag和TiO2纳米粒子与蒙脱石吸附作用示意图
Fig. 7. Schematic diagram of sorption of AgNPs and TiO2 NPs on montmorillonite
图 8 aSNPs和cMNPs异相共团聚的TEM照片(a)和SEM照片(b)
Fig. 8. TEM (a) and SEM (b) images of the heteroaggregates formed between the aSNPs and the cMNPs
图 9 原始状态ZnO纳米粒子TEM照片(a)以及在pH=6(b)和pH=8(c)的磷酸盐溶液(150 mg L-1)中熟化72 h后TEM照片
Fig. 9. TEM images of pristine ZnO NPs (a) and MNMs aged in 150 mg L-1 phosphate concentration for 72 h at pH=6 (b) and at pH=8 (c)
图 10 PDDA保护的CdSe/ZnS量子点在紫外光辐射3 h后溶出离子Cd和Se的浓度随腐殖酸浓度的变化
Fig. 10. Cd and Se release of PDDA-coated QDs as a function of HA concentration after 3 h UV irradiation
图 11 废水实验中收集的AgNP的相差明场扫描透射电镜(STEM)照片(a)和EDX图谱指示S/Ag比例随空间的变化(b)
据Kaegi et al.(2013).b.蓝色图谱指示左图篮框区域,红色图谱指示左图红色区域
Fig. 11. Phase contrast bright field scanning transmission electron microscopy (STEM) image of an AgNP collected from the sewer batch experiments (a) and EDX spectra revealing spatial variations in the S/Ag ratios (b)
图 12 纳米银与浓度递增的Na2S反应前后溶解速率的变化
据Levard et al.(2011).在0.01 mol/L NaNO3,pH=7溶解速率实验中初始纳米银浓度为1 000 mg·L-1
Fig. 12. Dissolution rate measurements of Ag-NPs before and after reaction with increasing concentrations of aqueous Na2S
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