无需墨粉仅靠光即可多次打印重写的纸张（修改稿）

诸平

图1  光打印可重写纸张样品

   据《物理学家组织网》(Phys.org)2017年2月2日报道，山东大学国家胶体材料工程技术研究中心的王文寿（Wenshou Wang）教授等人成功研制出不需要我们常用的激光打印机使用的碳粉,仅仅靠光照就可以进行打印，而且可以重复使用的纸张。此研究是山东大学国家胶体材料工程技术研究中心的王文寿（Wenshou Wang）教授与美国加州大学河滨分校（University of California, Riverside）和美国劳伦斯·伯克利国家实验室（Lawrence Berkeley National Laboratory）的研究人员合作完成的，实际上是2016年11月22日在美国化学会主办的Nano Letters网站发表的论文，详见：Wenshou Wang，Ji Feng, Yifan Ye, Fenglei Lyu, Yi-sheng Liu, Jinghua Guo, Yadong Yin.

Photocatalytic Color Switching of Transition Metal Hexacyanometalate Nanoparticles for High-Performance Light-Printable Rewritable Paper（点击可以免费下载）. Nano Letters. DOI: 10.1021/acs.nanolett.6b03909，Publication Date (Web): November 22, 2016. 2017年3月1日，The Conversation杂志网站也对此进行了报道（Read the original article）.

   众所周知，激光打印机不仅需要墨粉，而且需要纸张。但是纸张的生产不仅会对环境带来不良影响,而且如果以木质纤维作为造纸原材料，造纸也会对生态环境造成威胁，如果研究出可以重复使用的纸张，自然对于减少环境污染和生态威胁意义重大。王文寿等人的此项新研究成果，就是已经开发出一种利用紫外线，无需墨粉就可以进行打印的纸张,而且被打印过的纸张如果加热到120 ℃，不需要涂改液或者消字灵即可消除字迹，再次重新进行打印，可以如此重写80余次。用光打印的秘密源于纳米粒子的化学变色,其实就是在传统的纸张涂上一层薄薄的纳米微粒（约为纸张厚度的10^-5），即可轻而易举的将传统的纸转变成依靠光即可打印的纸张。下图就是光打印纸张若干张样品。

图2 各种不同光打印可重写样品（Various samples of the light-printable paper. Credit: Wang et al）

       加州大学河滨分校的化学教授殷亚东（Yadong Yin，也是此论文的通讯作者之一）告诉《物理学家组织网》（Phys.org）：“我们工作的最重要意义就是开发出了一种新类固态光转化色彩系统，无需墨粉靠光即可多次打印重写的纸张,这种新纸张与传统纸张相比较，外观给人的感觉并没有什么不同,但是它可以打印、并反复消除字迹而且不需要额外的墨粉,此项工作被认为在现代社会生活中，具有巨大的经济和环境价值。”因为目前纸的生产和处置对环境有很大的负面影响:造纸企业是工业污染的主要来源之一,废弃纸也是垃圾填埋场的主要组成部分(在美国大约占40%),就废纸回收而言，油墨去除的过程也会导致污染。除此之外，还有森林砍伐的问题:在美国,砍伐的树木当中约有三分之一的木材被用于纸张和纸板的生产。为了努力解决这些问题,研究人员一直在进行替代一次性纸的相关研究。一种可能性是利用某些化学物质暴光之后出现颜色转换特性,在过去这种方法面临稳定性、可逆性有限、成本高、毒性以及应用普通多孔涂层纸困难等诸多挑战。王文寿等人的研究成果，使这些问题得到解决，不需要墨粉，油墨污染问题就不复存在；靠光打印只需要很短的时间；而且可以反复使用80余次，使废纸处理量大大减少，所以应用前景广阔。如报纸、杂志、海报、记事本、写画架以及产品使用寿命标记、氧传感器等各种需要重写的标签都可以应用。

   新涂层包含两种类型的纳米粒子:一种是由普鲁士蓝（Prussian blue）组成,普鲁士蓝是一种常见的廉价、无毒蓝色色素,获得电子时为无色；另一种是二氧化钛(TiO₂)，纳米TiO₂是一种光催化剂材料，在紫外线照射下可以加速化学反应。将普鲁士蓝和TiO₂纳米颗粒均匀混合后涂到纸上,即可得到未打印的纸，此时纸面呈现出蓝色。为了打印文字或图像,需要将文字暴露于紫外线,光激发二氧化钛纳米颗粒使其释放电子，被邻近的普鲁士蓝纳米粒子接收,得到电子后普鲁士蓝由蓝色变为无色。

因为在无色背景条件下浏览蓝色文字与蓝色背景条件下浏览白色文字相比较，要更容易、更方便识别，但是也可以有其它不同的颜色，详见图2所示。需要说明的是一旦打印之后,在高分辨率(5-μm)的条件下，打印结果至少可以保留五天,然后会受到环境条件氧化作用的影响，逐渐变化又回到蓝色状态。如果需要更快地消除纸面的文字或图像,也可以加热10分钟即可使其返回到蓝色状态。研究者预测,此类光打印纸张如果以商业化规模进行生产，成本还会下降。因为这种特殊纸的生产工艺并不复杂，其实就是在传统纸张的表面进行涂饰,而且涂料价格便宜,涂饰过程简单。传统纸张的表面通过简单的过程,如浸泡或喷洒即可。印刷过程因为不需要墨，因此也比传统的印刷工艺更划算、更经济。最重要的是,可以重用超过80次,大大降低了总体成本。

更多信息请浏览原文

Abstract

Developing efficient photoreversible color switching systems for constructing rewritable paper is of significant practical interest owing to the potential environmental benefits including forest conservation, pollution reduction, and resource sustainability. Here we report that the color change associated with the redox chemistry of nanoparticles of Prussian blue and its analogues could be integrated with the photocatalytic activity of TiO2 nanoparticles to construct a class of new photoreversible color switching systems, which can be conveniently utilized for fabricating ink-free, light printable rewritable paper with various working colors. The current system also addresses the phase separation issue of the previous organic dye-based color switching system so that it can be conveniently applied to the surface of conventional paper to produce an ink-free light printable rewritable paper that has the same feel and appearance as the conventional paper. With its additional advantages such as excellent scalability and outstanding rewriting performance (reversibility >80 times, legible time >5 days, and resolution >5 μm), this novel system can serve as an eco-friendly alternative to regular paper in meeting the increasing global needs for environment protection and resource sustainability.

Keywords:

nanoparticles; photoreversible color switching; Prussian blue; Prussian blue analogues; rewritable paper; titania

殷亚东教授高引（>160次）论文

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