This work was partly supported by Nippon Sheet Glass Foundation for Materials Science and Engineering and JSPS KAKENHI (Grant-in-Aid for Challenging Exploratory Research, #50362281).

注意:化学品和解决方案时一定要小心。按照相应的安全实践和戴手套，眼镜和白大褂在任何时候。要知道，相比于他们的对手散装纳米材料可能有额外的危害。 1.摄政的制备<ol><li>制备通过溶解0.0012克1,1&#39;-二甲基-4,4&#39;-双吡啶鎓二氯化物的甲基紫精的水溶液;在20毫升水中，得到0.2mM的MV 2+（甲基紫精的MV 2+）。 </li><li>通过在10毫升的水0.1050克金（Ⅲ）四氯化三水合物（氯金酸4•3H 2 O） 的溶解，得到25mM的氯金酸4准备金（Ⅲ）氯化物水溶液。 </li><li>制备通过溶解0.03844克四氢硼酸钠在10毫升水的硼氢化钠水溶液（加入NaBH 4），得到100毫加入NaBH 4。 </li><li>准备由dissolv 2- ammoniumethanethiol水溶液ING0.2985克在25ml水中2- ammoniumethanethiol氯化物盐（2-AET +），得到100毫摩尔2- AET +。 </li></ol> 2. TNS胶体悬浮液的合成注:二氧化钛纳米片（TNS的Ti 0.91 O 2），分别按照既定的程序制备先前22,23,30报道。 <ol><li>通过煅烧铯2 CO 3（0.4040克）和TiO 2的化学计量混合物制备层状钛酸铯Cs的0.7的Ti 1.825 O 4的原料（ST-01;0.5000克）在800℃20小时22。重复此两次。 </li><li>制备质子化层状钛酸盐（H 0.7的Ti 1.825 O 4·H 2 O）通过用盐酸（100毫，81.42毫升）通过使用振动筛（300赫兹）12小时水溶液反复处理0.8142克钛酸铯。 </li><li>准备剥离的层状钛酸盐（TNS）胶体悬浮由在黑暗条件下环境温度的水溶液约2周-搅拌质子钛粉（0.0998克）大力（500转），用25毫升17毫米四丁基铵（TBA + OH）的。将所得乳白色悬浮液包含落二氧化钛纳米片（TNS 1.4克/升，pH值= 11〜12）。 </li></ol> 3. TNS 21薄膜的合成<ol><li> TNS的制备延薄膜（C-TNS） <ol><li>预清洁的玻璃基板（约20×20mm的2）通过使用在1M氢氧化钠水溶液（氢氧化钠）的超声波清洗器（27千赫）30分钟的超声波处理。 </li><li>冲洗用5-10毫升的超纯水（&lt;0.056μS-1）的基板。 </li><li> 3分钟浸在0.1M盐酸水溶液（HCl）的玻璃基板，用5-10毫升的超纯水漂洗。 </li><li>清洁通过在纯水中超声处理（27千赫）的衬底1小时，并然后用纯净水冲洗。干后用2-3分钟的吹风机（直到干）。 </li><li>铸于300微升等分试样在玻璃基板上的TNS的胶体悬浮液。 </li><li>干燥在60℃下2小时使用干烤箱，得到的c-TNS膜。 </li></ol></li><li> TNS烧结膜的制备（S-TNS） <ol><li>在500℃下实现的玻璃基片（S-TNS膜），烧结在空气中获得的c-TNS薄膜上的TNS部件的热固定3小时（加热从25至500℃，以6.8℃的速度/分钟），使用烘箱。 </li><li>重复该烧结过程两次。 </li></ol></li><li> 薄膜的制备 <ol><li>当S-TNS膜浸渍在溶液中，放置敷S-TNS膜以使其朝向对于所有实验程序的顶部。 </li><li>覆盖铝箔设置，以避免TNS的光反应开展黑暗条件下的所有实验。 </li></ol></li><li> 预甲基紫精（MV 2+）插TNS薄膜（TNS / MV 2+）的paration <ol><li>在培养皿中在黑暗条件下在室温（RT）下的MV 2+氯化盐的水溶液（0.2毫3毫升）7小时浸入一个s-TNS膜。 </li><li>在黑暗中使用烘箱〜1小时漂洗用超纯水（5-10毫升）并在空气中干燥得到的样品在60℃。 </li></ol></li><li> 金的制备（Ⅲ）插TNS薄膜（TNS /金（III）） <ol><li>在氯金酸4在培养皿中在RT黑暗条件下的水溶液中（25毫米，3毫升）3小时浸泡一个TNS / MV 2+膜。 </li><li>在黑暗中使用烘箱〜1小时漂洗用超纯水（5-10毫升）并在空气中干燥得到的样品在60℃。 </li></ol></li><li> TNS膜的夹层空间内的金纳米粒子的合成（TNS /金纳米粒子） <ol><li>在加入NaBH 4的水溶液浸入一个TNS /金（Ⅲ）膜</sub&gt;（0.1M，5ml）的培养皿在室温黑暗条件下0.5小时。 </li><li>在黑暗中使用烘箱〜1小时干燥空气中得到的薄膜在60℃。 </li></ol></li><li> 2 AET +插TNS薄膜的制备（TNS / 2-AET +） <ol><li>在培养皿中，在室温24小时（0.1M，3ml）中-在2-AET +氯的水溶液浸泡的s TNS膜。 </li><li>漂洗在黑暗中约1小时使用烘箱获得具有超纯水（5-10毫升）并在空气中干燥的薄膜在60℃下。 </li></ol></li><li> 金（Ⅲ）和2- AET +共插TNS薄膜（TNS / 2-AET + /金（III））。 <ol><li>在氯金酸4在室温3小时的水溶液（25毫，3毫升）浸入一个TNS / 2-AET +膜。 </li><li>在黑暗中使用烘箱〜1小时漂洗用超纯水（5-10毫升）并在空气中干燥得到的薄膜在60℃。 </li></ol></li><li> 金纳米粒子withi的合成ÑTNS / 2-AET +膜的层间空间（TNS / 2-AET + /金纳米粒子）。 <ol><li>在加入NaBH 4（0.1M，5ml）中的在培养皿中在RT黑暗条件下的水溶液中0.5小时浸泡一个TNS / 2-AET + /金（Ⅲ）膜。 </li><li>在黑暗中使用烘箱〜1小时漂洗用超纯水（5-10毫升）并在空气中干燥得到的薄膜在60℃。 </li></ol></li><li> 刻画 <ol><li>进行X射线衍射（XRD）使用具有单色的Cu-Kα辐射（λ= 0.15405 nm）的桌面X射线衍射分析21，在30千伏和15毫安操作。 </li><li>以能量色散X射线光谱仪（EDS）光谱21。 </li><li>采用多通道光检测器或稳态紫外可见（UV-VIS）吸收分光光度计记录紫外-可见吸收光谱使用透射模式21所制备的样品。 </li></ol></li></ol>

We have nothing to disclose.

这个手稿提供了原位合成TNS膜的层间空间内金粒子（AuNPs）的详细协议。这是在原位合成TNS的层间空间内金纳米粒子的第一份报告。此外，我们发现，2-AET +作品作为TNS的夹层内的AuNPs有效的保护试剂。这些方法杂交金纳米粒子和TNS透明薄膜。 TNS膜具有良好的光学透明性21是通过烧结工艺（S-TNS膜）合成，如在协议部分呈现。烧结过程重复所需的完全除去有机杂质。当有机杂质仍然存在，电影变成暗灰色。在此，烧结工艺重复两次作为典型的运行;然而，进一步的重复是允许的。 我们成功地合成金纳米粒子含有，使用两个intermediat分层TNS电影Ë薄膜（ 即 TNS / MV 2+和TNS / 2 + AET电影）。两个中间膜浸泡在水氯金酸溶液中，相当数量的黄金品种（一个金原子的空间占用是1.47-1.61纳米2）被安置在TNS膜的夹层空间内。这表明，在MV 2+和2- AET +分子作用在TNS层（ 图1B和图2A和表1）的作为有效扩展。然而，金物种进入TNS的夹层的详细吸附机理仍不清楚。 所获得的金（III）盐的膜浸泡在含水的NaBH 4溶液中，并将薄膜的颜色立即从清晰变为紫色（ 图4和6），表明金纳米粒子的TNS夹层内的形成。此外，含金纳米粒子-TNS片保持良好的光学跨明度（ 见图8A作为典型的例子），并凝聚在玻璃基板上，在含水的MV 2+，2- AET +和NaBH 4溶液浸泡也是如此。这些方法可以适用于其它的金属离子，如铜和银21。 当TNS / MV 2+膜用作中间，所述金纳米粒子的颜色30分钟（ 图6）内的变化，这表明金纳米粒子的TNS的层间空间内的聚集。然而，使用TNS / 2-AET +膜作为中间（ 图8）被有效地抑制了金纳米颗粒的聚集和颜色的变化。这表明，2-AET +分子工作的有效的保护试剂的TNS隔层，类似于在溶液中的金纳米颗粒中金纳米粒子。 合成TNS / 2-AET + /金纳米粒子是稳定的对氧和在590nm的特征的消光带是维持超过4个月。这样的性质和TNS夹层内的金纳米粒子的稳定性预计展示在催化，光催化，并具有成本效益的电浆设备的开发适用性。

各种贵金属纳米颗粒（的MNP）表现出特征的颜色或色调由于它们的局域型表面等离子体共振（LSPR）特性;因此，的MNP可以各种光学和/或光化学应用1-4中使用。最近，金属氧化物半导体（MOS）的光催化剂，如二氧化钛（TiO 2）和的MNP，组合已被彻底研究作为新型光催化剂5-14。然而，在许多情况下，存在该MOS表面上非常少量的MNP的，因为大多数的MOS颗粒具有相对低的表面积。另一方面，层状金属氧化物半导体（LMOSs）显示出光催化性能，还具有大的表面积，典型地几百平方米每一个LMOS 15-17的单位为g。此外，各种LMOSs具有插层性质（ 即，各种化学物质可被容纳他们的膨胀和大中间层的空间内）15-20。因此，具有的MNP和LMOSs的组合，预期相对大量的MNP都与半导体光催化剂杂交。 我们已经报道了铜纳米粒子（CuNPs）21改性活生物体的夹层空间内的原位合成第一，通过非常简单的步骤透明薄膜（二氧化钛纳米片TNS 16-30）。然而，尚未报道的合成方法的细节和其他贵金属的MNP和TNS杂种的表征。此外，TNS层内的CuNPs很容易被氧化和环境条件下，21脱色。因此，我们集中于金粒子（AuNPs），因为金纳米粒子被广泛用于各种光学，光化学，和催化的应用，并且预期他们将抗氧化3-5,7,8,10-14相对稳定，28,31,32。在这里，我们报告TNS和表演塔的夹层空间内金纳米粒子的合成ŧ2 ammoniumethanethiol（2-AET +; 图1插图）有效地工作，作为TNS的夹层内的金纳米粒子的保护剂。

<table><tbody><tr><td>Methyl viologen dichloride</td><td>Aldrich Chemical&amp;nbsp; Co., Inc.</td><td>1910-42-5</td><td></td></tr><tr><td>Tetrabutylammonium hydroxide</td><td>TCI</td><td>T1685</td><td></td></tr><tr><td>cesium carbonate</td><td>Kanto Chemical Co., Inc.</td><td>07184-33</td><td></td></tr><tr><td>anatase titanium dixoide</td><td>Ishihara Sangyo Ltd.</td><td>ST-01</td><td></td></tr><tr><td>hydrochloric acid</td><td>Junsei Chemical Co., Ltd.</td><td>20010-0350</td><td></td></tr><tr><td>sodium hydroxide</td><td>Junsei Chemical Co., Ltd.</td><td>195-13775</td><td></td></tr><tr><td>Tetrachloroauric(III) acid trihydrate</td><td>Kanto Chemical Co., Inc.</td><td>17044-60</td><td></td></tr><tr><td>sodium tetrahydroborate</td><td>Junsei Chemical Co., Ltd.</td><td>39245-1210</td><td></td></tr><tr><td>2-ammoniumethanethiol hydrochloride</td><td>TCI</td><td>A0296</td><td></td></tr><tr><td>Ultrapure water (0.056 &amp;micro;S/cm)</td><td></td><td></td><td>Milli-Q water purification system (Direct-Q&lt;sup&gt;&amp;reg;&lt;/sup&gt; 3UV, Millipore)</td></tr><tr><td>Microscope slide (Thickness: 1.0&amp;#8211;1.2 mm)</td><td>Matsunami glass Co., Ltd.</td><td></td><td></td></tr></tbody></table>

in situ synthesis of gold nanoparticles without aggregation in the interlayer space of layered titanate transparent films

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs within the interlayer space of semiconducting layered titania nanosheet (TNS) films was investigated here. Two types of intermediate films (i.e., TNS films containing methyl viologen (TNS/MV2+) and 2-ammoniumethanethiol (TNS/2-AET+)) were prepared. The two intermediate films were soaked in an aqueous tetrachloroauric(III) acid (HAuCl4) solution, whereby considerable amounts of Au(III) species were accommodated within the interlayer spaces of the TNS films. The two types of obtained films were then soaked in an aqueous sodium tetrahydroborate (NaBH4) solution, whereupon the color of the films immediately changed from colorless to purple, suggesting the formation of AuNPs within the TNS interlayer. When only TNS/MV2+ was used as the intermediate film, the color of the film gradually changed from metallic purple to dusty purple within 30 min, suggesting that aggregation of AuNPs had occurred. In contrast, this color change was suppressed by using the TNS/2-AET+ intermediate film, and the AuNPs were stabilized for over 4 months, as evidenced by the characteristic extinction (absorption and scattering) band from the AuNPs.

两种类型的前体薄膜在该研究中使用（ 即，具有和不具有所述保护试剂（2-AET +）TNS的夹层内）。在没有2-AET +，1,1&#39;-二甲基-4,4&#39;-双吡啶鎓二氯化物（甲基紫精; MV 2+）作为中间层的空间的膨胀，因为MV 2+含LMOSs已经常用作在来宾交换方法的中间体用于制备LMOSs 16,17,21,33-36。 金纳米粒子的合成，而不2 AET + 以获得金（Ⅲ）插TNS（TNS /金（III））膜，MV 2+插TNS（TNS / MV 2+）21,24,25,27,29膜在氯金酸的水溶液浸渍4英寸（25毫米24小时）。 TNS的内金物质的吸附用能量ð确认ispersive X射线光谱仪（EDS）分析，这为Ti和Au明确的信号;钛的原子比:金估计为1:0.08。基于起始质子化，层状钛酸盐的化学式（H 0.7的Ti 1.825 O 4）和表面电荷密度（0.307-0.366毫微米2每次充电）22，由一个金原子所占据的面积估计为1.47-1.61纳米2。因此，金原子的显著量容纳在TNS内。此外，检测到强烈的氯ķα信号和Au的原子比:氯估计为1:2.4的EDS分析±0.1（ 图2A）。这一结果意味着，不稳定四氯（Ⅲ）酸被部分分解，金物质被吸附上的TNS作为分解产物。然而，金（III）的分解和吸附机制的细节仍不清楚。我们假设金（III）与-OH基团，如AuC中配合L 3（OH）和AUCL 2（OH）2 37，形成在系统中，和Au物种的-OH基团可以通过与表面-OH基团的相互作用用Au物种的TNS的夹层内的吸附协助TNS 38。原始TNS / MV 2+和TNS /金（Ⅲ）的XRD轮廓分别示于图3A和3B。 X射线衍射分析的进一步的细节（ 即，衍射角，D（002）的值，和全宽在半最大值在d（FWHM）（002）的信号的研究的薄膜的）也总结在表1中。之前在氯金酸4溶液中浸泡，在7.82°和15.5°（D = 1.13纳米）为TNS / MV 2+膜观察到两个特性X射线衍射信号，表明该膜保留一个堆叠层结构，如先前报道21。当TNS / MV 2+片被浸泡在氯金酸</suB&gt;溶液中，两个特性X射线衍射信号被转移到一个更高的角度区域（D = 0.98纳米）。 TNS的一层的厚度被报告为0.75Ñ23,26,39,40，并且因此，在层之间的估计的距离（间隙空间; CLS）为0.23纳米。这意味着，TNS的层间空间内的MV 2+分子通过四氯（Ⅲ）酸或它的分解产物被取代的，如金（〜0.17纳米）41-43的离子直径比的MV 2+的更小的（分子大小:〜1.3纳米×0纳米）24。基于EDS和XRD分析，我们可以得出结论，金（Ⅲ）的TNS的层间空间中存在的物种。 所得到的TNS /金（Ⅲ）膜与加入NaBH含水4作为还原剂处理，并将加入NaBH 4 -处理的膜的X射线衍射剖面图3C所示。一个特点D（002）= 1.00纳米用峰值位置几乎相同的TNS /金（Ⅲ）膜（ 表1）的观察到的衍射信号。在加入NaBH 4 -处理的薄膜显示比上述TNS /金（Ⅲ）膜的更广泛的信号，这表明常规层叠结构变得在加入NaBH 4治疗紊乱。这些行为是相当类似，对于TNS和铜系统21观察到。 EDS分析表明，钛的原子比:金估计为1:0.09，这表明金物质没有从TNS解吸，即使是通过将水加入NaBH 4处理。此外，在EDS分析（ 图1B）中未检测到氯原子，这表明金（Ⅲ）物种可以定量地加入NaBH 4还原。处理后用NaBH 4的TNS /金（Ⅲ）膜，该膜的颜色立即从明确改变成金属紫色， 如图4A和4B所示 。一个新的广阔的灭绝（吸收和散射）带在400-600 nm处时加入NaBH 4 -处理观察到的， 如图5。薄膜的这种着色是与减速金（Ⅲ）通过加入NaBH 4处理21形成的TNS的层间空间内的金纳米粒子是一致的。所制备的NaBH 4 -处理的薄膜被允许在一个充气的NaBH 4溶液静置，并在膜的颜色从金属紫色逐渐改变为30分钟（ 图4C）内的透光性多尘的外观。在400〜600纳米的特征失效带还在30分钟内消失， 如图5 28。在这两个含氮或氧的饱和水溶液加入NaBH 4溶液中观察到类似的颜色变化， 如图6。由于颜色变化不是在氮气下抑制（N 2）气氛中，颜色变化并不预示t的范围内的金纳米粒子的氧化他夹层TNS的。这是相对于铜和TNS系统21; TNS的的层间内CuNPs立即被分子氧氧化。因此，这样的颜色变化表明了TNS 28,44的层间空间内的金纳米粒子的聚集。 带有2 AET +金纳米粒子的合成作为保护剂避免在TNS，2- AET +和在TNS薄膜的金物质进行了研究的共同嵌入的层间空间中的金纳米颗粒的聚集，因为烷基硫醇和烷基阳离子已频繁用作抗聚集保护试剂齐次解45,46内金纳米粒子和层间化合物16,17,34,47，分别为助理试剂。要获得2 + AET插（TNS / 2-AET +）薄膜，烧结TNS（S-TNS）在电影2 AET +水溶液浸泡。的s TNS和TNS / 2-AET +薄膜的XRD轮廓分别示于图1A和1B。起始S-TNS薄膜呈现在9.92°（D = 0.89 nm）的特征d（002）信号。当与含水2- AET +治疗，对d（002）的信号被转移到一个较低的角为d = 1.08纳米，和一个新的D（004）的信号出现了。 CLS的估计为0.33纳米（ 表1）。相比于起始S-TNS膜，TNS / 2-AET +的观察D（002）信号变得激烈而窄，指示该堆叠结构变得排序。这些结果表明，2-AET +分子嵌入到TNS层。 2-AET +分子可能会在一个反平行单层方式定向并相对于TNS片倾斜，因为估计CLS是略微小呃比为2 AET +（〜0.4纳米）16,17的分子长度。 2-AET +的所提出的结构-处理的TNS（TNS / 2-AET +）的图7A中示出。 TNS的/ 2-AET +薄膜在氯金酸中浸泡4水溶液3小时，其结果是发生了特征d偏移到更高的角度（002）的信号，指示层的距离的该收缩率（ 图1C和表1 ）。根据EDS分析中检测到黄金和氯原子的一个显著量（钛:金= 1:0.02和Au:CL = 1:0.4），这表明金（Ⅲ）的原子是在TNS的层插和起始的那部分四氯（Ⅲ）的酸可以在实验程序已分解。的氯金酸4 -处理的膜的估计CLS为0.25纳米，且CLS比原始TNS / 2-AET稍小<sup&gt; +（ΔD = 0.08纳米）。然而，CLS比金的离子直径（〜0.17纳米）的显著大。此外，对应于NH两个宽和特征信号（3,100-3,200和3,300-3,450厘米-1）的FT-IR测定检测拉伸。这一结果表明，2-AET +分子留在TNS的层间空间。 X射线衍射，EDS，和FT-IR分析暗示两个-2- AET +和金（Ⅲ）的TNS的层间内被嵌入，以及含有该TNS的所提出的结构2-AET +和金（Ⅲ）（TNS / 2-AET + /金（III））示于图7B。 TNS / 2-AET + /金（Ⅲ）膜浸泡于30分钟将水加入NaBH 4溶液，在此期间薄膜的颜色由透明变为微红， 如图8A所示 。该硼氢化钠的灭绝和差分光谱<suB&gt; 4 -处理的TNS / 2-AET + /金（Ⅲ）膜分别示于图9和图 8B。在加入NaBH 4处理，观察在λ 最大 = 590纳米的明确消光带，并且所观察到的消光带最大值是相似的金纳米粒子的在TiO 2 5,48或TNS 28的层间空间内的LSPR频带。佃等。已经报道的Au（I）的形成-thiolate复杂49。然而，我们预测，大多数的Au原子被完全加入NaBH 4还原TNS / 2-AET +在本状态下的中间层内，由于消光频谱形状是在层间空间类似于独立合成的Au（0）纳米粒子的TNS的28。此外，广角X射线衍射表明，形成的结晶金种类的，如下所述。 X射线衍射分析表明对d（002）的信号变得更加广泛和稍微偏移到一个较低的角的NaBH 4处理（ 图1D和表1）后，这表明常规层叠结构变得在加入NaBH 4治疗紊乱。钛的估计的原子比:金为1:0.02，这表明金物质没有从TNS / 2-AET +水加入NaBH 4处理期间解吸。这些行为是非常相似的那些TNS / CuNPs和TNS /金纳米粒子观察到的，如先前所述。 各种TNS膜的广角X射线衍射剖面和对应于金晶体（PDF:00-001-1174）的反射显示在图10。在开始S-TNS膜的情况下，对应于钛两个弱衍射信号在37.8°和48.2°（ 图10a）中观察到1.825õ0.175表。同样的衍射信号我们重也观察到了TNS / 2-AET +膜的峰位置相同，起始S-TNS膜的（ 图10b）。新特性X射线衍射信号出现在38.3°和44.5°的加入NaBH 4 -处理的TNS / 2-AET + /金（Ⅲ）膜， 如图10d中所示。然而，在37.8°和48.2°的TNS张衍射信号被保留不变。在38.3°和44.5°的新出现的X射线衍射信号是相当类似的对于d（111）和d（200）衍射从结晶金。这一结果意味着，结晶金（ 即，金纳米粒子）进行TNS的层间空间内产生。然而，奇怪的是，这两个特性X射线衍射信号出现在TNS / 2-AET + /金（Ⅲ）膜，尽管非治疗的NaBH 4（ 图10c），和金种类的应保持作为金（Ⅲ） 。类似怪异的行为也Øbserved为前和NaBH 4处理后的TNS /金（Ⅲ）， 如图11。这种行为的起源尚不清楚;但是，我们假定在半导体和/或TNS的催化性能影响而不加入NaBH 4处理该Au-结晶形成，或许漏光或X射线诱发50,51减少Au的微量的形成。基于灭绝，XRD，和EDS分析，我们可以得出结论，TNS片的层间（ 即 TNS / 2-AET + /金纳米粒子薄膜）通过程序提交成功制备内形成金纳米粒子。此外，所观察到的消光带最大值表明金纳米粒子可能被分离。因此，TNS的层间空间内-2- AET +被认为是形成有所述金纳米粒子的有效的保护试剂。 金纳米粒子在TNS层下AMB 2 AET +的稳定性ient气氛灭绝频谱分析证实。透射灭绝和两种类型的TNS / 2-AET + /金纳米粒子膜的微分谱（ 即作为制备和5分钟的NaBH 4处理的内，以及在黑暗条件下在充气气氛静置124天之后）示于图12。未观察到光谱变化为消光光谱，即使经过4个月，这表明TNS内的金纳米粒子用2- AET +反对氧稳定。 TNS膜内金纳米粒子该等稳定价格有望在成本效益等离子催化剂的开发表现出极大的适用性。 <img alt="图1" src="/files/ftp_upload/55169/55169fig1.jpg" /> 图1:S-TNS（A），TNS / 2-AET +（B）的XRD轮廓，TNS / 2-AET + /金（III）（C）中，ð加入NaBH 4 -处理的TNS / 2-AET + /金（Ⅲ）（TNS / 2-AET + /金纳米粒子）（D）的膜。插图示出2-AET +的化学式。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图2" src="/files/ftp_upload/55169/55169fig2.jpg" /> 图2:TNS /金（III）（A）和硼氢化钠的EDS谱-处理TNS /金（III）（B）薄膜。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图3" src="/files/ftp_upload/55169/55169fig3.jpg" /> 图3:在TNS / MV 2+（A）的XRD轮廓，TNS /金（III）（&lt;STRONG&gt; B）和硼氢化钠-处理TNS /金（III）（C）薄膜。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig3large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图4" src="/files/ftp_upload/55169/55169fig4.jpg" /> 图4:各种TNS和金杂化膜的照片:TNS /金（Ⅲ）（A）和NaBH 4 -处理的TNS /金（Ⅲ）在充气的NaBH 4水溶液1分钟（B）和30分钟（C）的范围内的薄膜解决方案。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig4large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图5" src="/files/ftp_upload/55169/55169fig5.jpg" /> 图5:消光的光谱变化硼氢化钠-处理TNS /金（III）薄膜充气的硼氢化钠溶液1-30分钟。的箭头表示在400-600毫微米的消光谱带的消失。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig5large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图6" src="/files/ftp_upload/55169/55169fig6.jpg" /> 图6:加入NaBH 4的照片-处理的TNS /金（Ⅲ）中的各种气体饱和的NaBH 4水溶液膜:（A）氧气，（B）的氮，和（C）的空气。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig6large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图7" src="/files/ftp_upload/55169/55169fig7.jpg" /> Figu<html>重新7:TNS / 2 + AET（A）和氯金酸的建议-处理示意图TNS / 2 + AET（TNS / 2 + AET /金（III））（B）薄膜。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig7large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图8" src="/files/ftp_upload/55169/55169fig8.jpg" /> 图8:（A）中的TNS / 2-AET + /金（Ⅲ）的照片（上图）和NaBH 4 -处理的膜（底部）。 （B）中的NaBH 4的微分消光光谱-处理的TNS / 2-AET + /金（Ⅲ）膜。频谱是通过考虑TNS / 2-AET + /金（Ⅲ）膜作为背景光谱和从加入NaBH 4处理后得到的频谱中减去归一化。/55169fig8large.jpg"目标="_空白"&gt;点击此处查看该图的放大版本。 <img alt="图9" src="/files/ftp_upload/55169/55169fig9.jpg" /> 图9:TNS / 2-AET + /金（Ⅲ）的透射消光光谱（黑色）和NaBH 4 -处理的TNS / 2-AET + /金（III）（红色）膜。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig9large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图10" src="/files/ftp_upload/55169/55169fig10.jpg" /> 图10:S-TNS（a） 中 ，TNS / 2-AET +（b）中 ，TNS / 2-AET + /金（III）（ 三 ）的广角X射线衍射剖面，和NaBH 4 -处理的TNS / 2 -AET + /金（Ⅲ）（ 四 ）膜，以及在PDF的索引晶金。实心圆圈表示由Ti 1.825 0.175Ø张衍射。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig10large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图11" src="/files/ftp_upload/55169/55169fig11.jpg" /> 图11:TNS /金（Ⅲ）（ 一 ）和NaBH 4的广角X射线衍射剖面-处理的TNS /金（Ⅲ）（B）的薄膜。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig11large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图12" src="/files/ftp_upload/55169/55169fig12.jpg" /> 图12:TNS / 2-AET + /金纳米粒子膜的微分消光光谱:所制备的（a）和静置后124天加气和黑暗条件下（B）。该光谱通过减去TNS / 2-AET + /金（Ⅲ）膜作为背景光谱归一化。 <a href="https://ecsource-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/55169/55169fig12large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="表格1" src="/files/ftp_upload/55169/table1.jpg" /> 表1:衍射角（2θ），D值，D的FWHM（002）信号的XRD轮廓，以及投资的电影估计间隙空间（CLSS）。

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In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

在这里，我们提出了一个协议为原位合成层状钛酸盐薄膜的夹层空间内的黄金纳米粒子（纳米金）的无金纳米颗粒的聚集。即使4个月后没有观察到的光谱变化。合成的材料已预期在催化，光催化，并具有成本效益的电浆设备的开发应用程序。

在没有聚集的层状钛酸盐薄膜透明的层间金纳米粒子的原位合成

Combinations of metal oxide semiconductors and gold nanoparticles (AuNPs) have been investigated as new types of materials. The in situ synthesis of AuNPs ...

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In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

8.0K 次观看.  Niigata University. 在这里，我们提出了一个协议为原位合成层状钛酸盐薄膜的夹层空间内的黄金纳米粒子（纳米金）的无金纳米颗粒的聚集。即使4个月后没有观察到的光谱变化。合成的材料已预期在催化，光催化，并具有成本效益的电浆设备的开发应用程序。 

视频: In Situ Synthesis of Gold Nanoparticles without Aggregation in the Interlayer Space of Layered Titanate Transparent Films

Template Directed Synthesis of Plasmonic Gold Nanotubes with Tunable IR Absorbance

A nearly parallel array of pores can be produced by anodizing aluminum foils in acidic environments1, 2. Applications of anodic aluminum oxide (AAO) membranes have been under development since the 1990's and have become a common method to template the synthesis of high aspect ratio nanostructures, mostly by electrochemical growth or pore-wetting. Recently, these membranes have become commercially available in a wide range of pore sizes and densities, leading to an extensive library of functional nanostructures being synthesized from AAO membranes. These include composite nanorods, nanowires and nanotubes made of metals, inorganic materials or polymers 3-10. Nanoporous membranes have been used to synthesize nanoparticle and nanotube arrays that perform well as refractive index sensors, plasmonic biosensors, or surface enhanced Raman spectroscopy (SERS) substrates 11-16, as well as a wide range of other fields such as photo-thermal heating 17, permselective transport 18, 19, catalysis 20, microfluidics 21, and electrochemical sensing 22, 23. Here, we report a novel procedure to prepare gold nanotubes in AAO membranes. Hollow nanostructures have potential application in plasmonic and SERS sensing, and we anticipate these gold nanotubes will allow for high sensitivity and strong plasmon signals, arising from decreased material dampening 15.

Solution-suspendable gold nanotubes with controlled dimensions can be synthesized by electrochemical deposition in porous anodic aluminum oxide (AAO) membranes using a hydrophobic polymer core. Gold nanotubes and nanotube arrays hold promise for applications in plasmonic biosensing, surface-enhanced Raman spectroscopy, photo-thermal heating, ionic and molecular transport, microfluidics, catalysis and electrochemical sensing.

的模板导演电浆黄金纳米管的合成与可调谐红外吸收

A nearly parallel array of pores can be produced by anodizing aluminum foils in acidic environments1, 2. Applications of anodic aluminum oxide (AAO) ...

科研

化学

A Technique to Functionalize and Self-assemble Macroscopic Nanoparticle-ligand Monolayer Films onto Template-free Substrates

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and scalable technique efficiently functionalizes metallic nanoparticles with thiol-ligands in a miscible water/organic solvent mixture allowing for rapid grafting of thiol groups onto the gold nanoparticle surface. The hydrophobic ligands on the nanoparticles then quickly phase separate the nanoparticles from the aqueous based suspension and confine them to the air-fluid interface. This drives the ligand-capped nanoparticles to form monolayer domains at the air-fluid interface.&#160; The use of water-miscible organic solvents is important as it enables the transport of the nanoparticles from the interface onto template-free substrates.&#160; The flow is mediated by a surface tension gradient3,4 and creates macroscopic, high-density, monolayer nanoparticle-ligand films.&#160; This self-assembly technique may be generalized to include the use of particles of different compositions, size, and shape and may lead to an efficient assembly method to produce low-cost, macroscopic, high-density, monolayer nanoparticle films for wide-spread applications.

A simple, robust and scalable technique to functionalize and self-assemble macroscopic nanoparticle-ligand monolayer films onto template-free substrates is described in this protocol.

一种技术，功能化和自组装纳米宏观 - 配体单层膜模板上无基材

This protocol describes a self-assembly technique to create macroscopic monolayer films composed of ligand-coated nanoparticles1,2. The simple, robust and ...

Synthesis, Assembly, and Characterization of Monolayer Protected Gold Nanoparticle Films for Protein Monolayer Electrochemistry

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently incorporated into film assemblies that serve as adsorption platforms for protein monolayer electrochemistry (PME). PME is utilized as the model system for studying electrochemical properties of redox proteins by confining them to an adsorption platform at a modified electrode, which also serves as a redox partner for electron transfer (ET) reactions. Studies have shown that gold nanoparticle film assemblies of this nature provide for a more homogeneous protein adsorption environment and promote ET without distance dependence compared to the more traditional systems modified with alkanethiol self-assembled monolayers (SAM).1-3 In this paper, MPCs functionalized with hexanethiolate ligands are synthesized using a modified Brust reaction4 and characterized with ultraviolet visible (UV-Vis) spectroscopy, transmission electron microscopy (TEM), and proton (1H) nuclear magnetic resonance (NMR). MPC films are assembled on SAM modified gold electrode interfaces by using a "dip cycle" method of alternating MPC layers and dithiol linking molecules. Film growth at gold electrode is tracked electrochemically by measuring changes to the double layer charging current of the system. Analogous films assembled on silane modified glass slides allow for optical monitoring of film growth and cross-sectional TEM analysis provides an estimated film thickness. During film assembly, manipulation of the MPC ligand protection as well as the interparticle linkage mechanism allow for networked films, that are readily adaptable, to interface with redox protein having different adsorption mechanism. For example, Pseudomonas aeruginosa azurin (AZ) can be adsorbed hydrophobically to dithiol-linked films of hexanethiolate MPCs and cytochrome c (cyt c) can be immobilized electrostatically at a carboxylic acid modified MPC interfacial layer. In this report, we focus on the film protocol for the AZ system exclusively. Investigations involving the adsorption of proteins on MPC modified synthetic platforms could further the understanding of interactions between biomolecules and man-made materials, and consequently aid the development of biosensor schemes, ET modeling systems, and synthetic biocompatible materials.5-8

Alkanethiolate stabilized gold colloids known as monolayer protected clusters (MPCs) are synthesized, characterized, and assembled into thin films as an adsorption interface for protein monolayer electrochemistry of simple redox protein like Pseudomonas aeruginosa azurin (AZ) and cytochrome c (cyt c).

单层的合成，装配和表征蛋白质单分子膜的电化学保护的金纳米粒子薄膜

Colloidal gold nanoparticles protected with alkanethiolate ligands called monolayer protected gold clusters (MPCs) are synthesized and subsequently ...

生物工程

Synthesis and Catalytic Performance of Gold Intercalated in the Walls of Mesoporous Silica

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties of the materials were investigated. We used a one pot sol-gel approach to intercalate gold nano particles in the walls of mesoporous silica. To start with the synthesis, P123 was used as template to form micelles. Then TESPTS was used as a surface modification agent to intercalate gold nano particles. Following this process, TEOS was added in as a silica source which underwent a polymerization process in acid environment. After hydrothermal processing and calcination, the final product was acquired. Several techniques were utilized to characterize the porosity, morphology and structure of the gold intercalated mesoporous silica. The results showed a stable structure of mesoporous silica after gold intercalation. Through the oxidation of benzyl alcohol as a benchmark reaction, the GMS materials showed high selectivity and recyclability.

Here, we present a protocol with a sol-gel process to synthesize gold intercalated in the walls of mesoporous materials (GMS), which is confirmed to possess a mesoporous matrix with gold intercalated in the walls imparting great stability and recyclability.

合成和金插在介孔二氧化硅的墙壁催化性能

As a promising catalytically active nano reactor, gold nanoparticles intercalated in mesoporous silica (GMS) were successfully synthesized and properties ...

Gold Nanostar Synthesis with a Silver Seed Mediated Growth Method

The physical, chemical and optical properties of nano-scale colloids depend on their material composition, size and shape 1-5. There is a great interest in using nano-colloids for photo-thermal ablation, drug delivery and many other biomedical applications 6. Gold is particularly used because of its low toxicity 7-9. A property of metal nano-colloids is that they can have a strong surface plasmon resonance 10. The peak of the surface plasmon resonance mode depends on the structure and composition of the metal nano-colloids. Since the surface plasmon resonance mode is stimulated with light there is a need to have the peak absorbance in the near infrared where biological tissue transmissivity is maximal 11, 12.
We present a method to synthesize star shaped colloidal gold, also known as star shaped nanoparticles 13-15 or nanostars 16. This method is based on a solution containing silver seeds that are used as the nucleating agent for anisotropic growth of gold colloids 17-22. Scanning electron microscopy (SEM) analysis of the resulting gold colloid showed that 70 % of the nanostructures were nanostars. The other 30 % of the particles were amorphous clusters of decahedra and rhomboids. The absorbance peak of the nanostars was detected to be in the near infrared (840 nm). Thus, our method produces gold nanostars suitable for biomedical applications, particularly for photo-thermal ablation.

We synthesized star shaped gold nanostars using a silver seed mediated growth method. The diameter of the nanostars ranges from 200 to 300 nm and the number of tips vary from 7 to 10. The nanoparticles have a broad surface plasmon resonance mode centered in the near infrared.

黄金Nanostar合成银种子介导的生长方法

The physical, chemical and optical properties of nano-scale colloids depend on their material composition, size and shape 1-5. There is a great interest ...

Synthesis and Reaction Chemistry of Nanosize Monosodium Titanate

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the material with Au(III) ions. The synthesis method was derived from a sol-gel process used to produce micron-sized monosodium titanate (MST), with several key modifications, including altering reagent concentrations, omitting a particle seed step, and introducing a non-ionic surfactant to facilitate control of particle formation and growth. The resultant nMST material exhibits spherical-shaped particle morphology with a monodisperse distribution of particle diameters in the range from 100 to 150&#160;nm. The nMST material was found to have a Brunauer-Emmett-Teller (BET) surface area of 285 m2g-1, which is more than an order of magnitude higher than the micron-sized MST. The isoelectric point of the nMST measured 3.34 pH units, which is a pH unit lower than that measured for the micron-size MST. The nMST material was found to serve as an effective ion exchanger under weakly acidic conditions for the preparation of an Au(III)-exchange nanotitanate. In addition, the formation of the corresponding peroxotitanate was demonstrated by reaction of the nMST with hydrogen peroxide.

The surfactant mediated sol-gel synthesis of nanosized monosodium titanate is described, along with preparation of the corresponding peroxide modified material. An ion-exchange reaction with Au(III) is also presented.

纳米尺寸钛酸二氢钠的合成和化学反应

This paper describes the synthesis and peroxide-modification of nanosize monosodium titanate (nMST), along with an ion-exchange reaction to load the ...

A Simple Method for the Size Controlled Synthesis of Stable Oligomeric Clusters of Gold Nanoparticles under Ambient Conditions

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like oligomeric clusters of these yellow nanoparticles of narrow size distribution are synthesized under ambient conditions via two methods. The delay-time method controls the number of subunits in the oligoclusters by varying the time between the addition of HAuCl4 to alkaline solution and the subsequent addition of reducing agent, NaSCN. The yellow oligoclusters produced range in size from ~3 to ~25 nm. This size range can be further extended by an add-on method utilizing hydroxylated gold chloride (Na+[Au(OH4-x)Clx]-) to auto-catalytically increase the number of subunits in the as-synthesized oligocluster nanoparticles, providing a total range of 3 nm to 70 nm. The crude oligocluster preparations display narrow size distributions and do not require further fractionation for most purposes. The oligoclusters formed can be concentrated &#62;300 fold without aggregation and the crude reaction mixtures remain stable for weeks without further processing. Because these oligomeric clusters can be concentrated before derivatization they allow expensive derivatizing agents to be used economically. In addition, we present two models by which predictions of particle size can be made with great accuracy.

We describe a simple method for producing highly stable oligomeric clusters of gold nanoparticles via the reduction of chloroauric acid (HAuCl4) with sodium thiocyanate (NaSCN). The oligoclusters have a narrow size distribution and can be produced with a wide range of sizes and surface coats.

根据环境条件的金纳米粒子的稳定低聚簇的大小控制合成的一种简便方法

Reducing dilute aqueous HAuCl4 with sodium thiocyanate (NaSCN) under alkaline conditions produces 2 to 3 nm diameter nanoparticles. Stable grape-like ...

Large Area Substrate-Based Nanofabrication of Controllable and Customizable Gold Nanoparticles Via Capped Dewetting

Recent scientific advances in the utilization of metallic nanoparticle for enhanced energy conversion efficiency, improved optical device performance, and high-density data storage have demonstrated the potential benefit of their use in industrial applications. These applications require precise control over nanoparticle size, spacing, and sometimes shape. These requirements have resulted in the use of time and cost intensive processing steps to produce nanoparticles, thus making the transition to industrial application unrealistic. This protocol will resolve this issue by providing a scalable and affordable method for the large-area production of nanoparticle films with improved nanoparticle control compared to the current techniques. In this article, the process will be demonstrated with gold, but other metals can also be used.

This protocol details a novel nano-manufacturing technique that can be used to make controllable and customizable nanoparticle films over large areas based on the self-assembly of dewetting of capped metal films.

大面积地下纳米化的可控、可定制金纳米粒子通过包盖湿法

Recent scientific advances in the utilization of metallic nanoparticle for enhanced energy conversion efficiency, improved optical device performance, and ...

工程学

Growth of Gold Dendritic Nanoforests on Titanium Nitride-coated Silicon Substrates

In this study, a high-power impulse magnetron sputtering system is used to coat a flat and firm titanium nitride (TiN) film on silicon (Si) wafers, and a fluoride-assisted galvanic replacement reaction (FAGRR) is employed for the rapid and easy deposition of gold dendritic nanoforests (Au DNFs) on the TiN/Si substrates. Scanning electron microscopy (SEM) images and energy-dispersive X-ray spectroscopy patterns of TiN/Si and Au DNFs/TiN/Si samples validate that the synthesis process is accurately controlled. Under the reaction conditions in this study, the thickness of the Au DNFs increases linearly to 5.10 &#177; 0.20 &#181;m within 15 min of the reaction. Therefore, the employed synthesis procedure is a simple and rapid approach for preparing Au DNFs/TiN/Si composites.

This study presents a feasible procedure for synthesizing gold dendritic nanoforests on titanium nitride/silicon substrates. The thickness of gold dendritic nanoforests increases linearly within 15 min of a synthesis reaction.

氮化钛涂层硅基板上金石榴石的生长

In this study, a high-power impulse magnetron sputtering system is used to coat a flat and firm titanium nitride (TiN) film on silicon (Si) wafers, and a ...

Gold Nanoparticle Synthesis

Gold nanoparticles (Au nanoparticles) that are ~12 nm in diameter were synthesized by rapidly injecting a solution of 150 mg (0.15 mmol) of tetrachloroauric acid in 3.0 g (3.7 mmol, 3.6 mL) of oleylamine (technical grade) and 3.0 mL of toluene into a boiling solution of 5.1 g (6.4 mmol, 8.7 mL) of oleylamine in 147 mL of toluene. While boiling and mixing the reaction solution for 2 hours, the color of the reaction mixture changed from clear, to light yellow, to light pink, and then slowly to dark red. The heat was then turned off, and the solution was allowed to gradually cool down to room temperature for 1 hour. The gold nanoparticles were then collected and separated from the solution using a centrifuge and washed three times; by vortexing and dispersing the gold nanoparticles in 10 mL portions of toluene, and then precipitating the gold nanoparticles by adding 40 mL portions of methanol and spinning them in a centrifuge. The solution was then decanted to remove any remaining byproducts and unreacted starting materials. Drying the gold nanoparticles in a vacuum environment produced a solid black pellet; which could be stored for long periods of time (up to one year) for later use, and then redissolved in organic solvents such as toluene.

A protocol for synthesizing ~12 nm diameter gold nanoparticles (Au nanoparticles) in an organic solvent is presented. The gold nanoparticles are capped with oleylamine ligands to prevent agglomeration. The gold nanoparticles are soluble in organic solvents such as toluene.