化學

鹼性電池使用的電解液均為強鹼，電池中的鋅極會與其發生腐蝕反應，使得電池放電壽命降低，並產生氫氣，而大量氫氣使得電池有爆裂的危險，為了改善上述問題，我們自行設計了氣體觀測儀器，用來檢測銀鋅電池充放電與靜置時之氣體產生量，更藉由探討影響變因的過程找出銀鋅電池較合適之使用條件，其中包含電解液種類及濃度之選擇、電極面積與充電電流對使用效果之影響，並改善電池腐蝕程度；我們將鋅極以浸鍍處理(Sn:Pb ＝1:1 )並搭配電解液添加物(KOH:Zn(OH)42 －＝ 2:1) 可效率地抑制氣體產生；更用氯化銀粉末取代傳統氧化銀極片為正極，發現氯化銀可代替氧化銀電極，且有不錯的放電效果。;As we know, the electrolyte solution used in an alkalinebattery is a concentrated alkaline solution, which corrodes the zinc electrode in a battery of this kind. The corrosive reaction not only reduces the lifespan of the battery but also produces hydrogen, causing the battery to explode. This study is intended to help us design a device to measure the quantity of hydrogen gas generated in the charging of a zinc-silver battery. We have studied several factors affecting zinc-silver battery, including the variety of electrolyte, the concentration of alkaline solution, the surface of electrode, and the density of charging current, etc. To reduce the corrosion of zinc electrode, we plate the zinc electrode by the immersion electroless plating method, using several kinds of low-polluting anti-corrosive additives (metallic compounds such as lead and tin). We also add zincate ion into electrolyte solution to further reduce the quantity of hydrogen produced. The experiments show a zinc-silver alkaline battery works most efficiently, if the powder of silver chloride is used instead of silver oxide.

近年來重金屬污染問題日益嚴重，因此檢測地下水、工業廢水中的重金屬含量為一重要課題。本實驗即是利用錄音機中的零件－石英振盪器作為電化學分析偵測的工作電極，在0.1 M KNO3（pH = 3）溶液中利用循環伏安法以50 mV/s 的掃描速度從 – 100 到 – 700 mV 持續掃描 10 圈，來穩定電極表面。 以方波陽極剝除伏安法（SWASV）模式設定預濃縮電位– 700 mV、預濃縮時間60 秒偵測重金屬的鉛離子。掃描電位範圍由 – 700 到 – 100 mV vs. Ag/AgCl 往氧化方向掃描。偵測鉛離子濃度範圍為200－600 ppb，之後可針對各種條件作最佳化的條件探討可降低偵測濃度及實際運用於地下水及工業廢水的檢測。 Heavy metal pollution becomes very serious. Lead (Pb) determination is a continuous research interest in clinical, environmental, and industrial application. The main causes for living biological media are mutagenic, carcinogenic, and teratogenic activity. The determination of trace metal in the ground and industrial waste water will be a important project. Here, we report a simple system which using quartz crystal microbalance (QCM) (use in radio machine) for working electrode. The QCM was first equilibrated in 0.1 M KNO3（pH = 3）base electrolyte for about 1 min before electrochemical experiments. It was then pretreated by continuous scans in the window from – 100 to – 700 mV at a scan rate of 50 mV/s until a stable background current obtained. The amount of Pb2+ was detected quantitatively using square-wave anodic stripping voltammetry（SWASV）. The potential range was set from – 100 to – 700 mV in the cathodic direction for most cases. The standard addition method concentration range is from 200 to 600 ppb. Analytical conditions were systematically optimized and extended to practical applications aslo.

The highly water-absorbing polymers were prepared by the reaction of acrylic acid as a graft\r monomer and natural starch (eg. rice starch, sticky rice starch or corn starch) as the backbone\r using water hydrogen peroxide and vitamin C as solvent, initiator and catalyst, respectively. The\r reaction was carried out by mixing of starch in distilling water and stirring at 60-70 ℃ for 3\r hours and then cooled to 30℃ Acrylic acid was added and the pH was adjusted to 6-9 by the\r addition of limestone powder. To the stirred mixture were then added hydrogen peroxide (30%\r v/v) and vitamin C and continued stirring for 3 hours until the solution became viscous The\r viscous solution was neutralized with potassium hydroxide (30%v/v) to give the pH for 6.5-7\r and allowed to cool to room temperature overnight. The resulting solution was spread on\r winnowing baskets and allowed to dry under the sun to yield a continuous absorbent polymer\r film. The absorbent polymer film was ground and yield of white powder, The above procedure\r was repeated by using another types of starch. The ability of starch slurry to swell on heating, by\r absorption of water, is it’s most important practical property. Rice starch has very low swelling\r capacity in aqueous media compare with sticky rice starch and corn starch. The capacities of\r water-absorbing polymer were tested by placing polymer powder in the beaker and adding of\r water until it swell and cannot absorb more water. The polymers were found to be an excellent\r water absorbent, which absorbed water about 248, 245 and 167 times in weight of polymer for\r corn starch, sticky rice starch and rice starch, respectively. The water retention was calculated by\r measuring the amount of water releasing after every week for 10 weeks. They have also good\r water retention capacity. The swollen polymers were mixed with soil in ratio 1:3 and the\r increasing water holding capacity of soils which promotes more efficient plant growth in pot were\r test. It was found that the soil could be absorbed water for 10 weeks. It is possible to use highly\r water-absorbing polymers from natural starch in agriculture because they are low in cost and the\r polysaccharide main portion of the product is biodegradable

本研究開發以天然資材為原料之綠色微型微生物燃料電池。電池以碳紙為陰陽極，陽極槽以酵母菌對葡萄糖之厭氣氧化反應，陰極則塗佈有葉綠素鐵傳遞電子，以催化氧氣的還原反應，使電之進行，成功的以修飾中心金屬離子後的葉綠素取代傳統微生物燃料電池使用的金屬卟啉類化合物。實驗發現，陽極以每克酵母菌溶以1.5mL的葡萄糖液進行氧化，將葉綠素鐵0.1g塗佈於陰極，並加入純水，曝於自然光，即可有效增加微生物燃料電池電壓，電壓可達0.62 V，與典型的燃料電池在全額負載下可產生的 0.5 - 0.8 V 相當，顯示出所開發的微型微生物燃料電池是具有應用潛力。為了提升所開發電池的實用性，將微生物燃料電池微型化設計便於攜帶及未來直接結合植物光合作用之組合，同時發展不需使用具毒性之電子傳遞介質的陽極反應，使能連續從植物光合作用取得葡萄糖作為燃料的可行性。本研究所開發的微型微生物燃料電池構造簡單，所使用的酵母菌、葡萄糖、葉綠素及氧氣等資材皆可於自然界取得，符合永續經營與綠色能源的目的。未來結合直接採用植物光合作用產生之葡萄糖為燃料來發電，更可發展為就地使用完全無污染的綠色植物太陽能源。

本研究將探討所合成的金屬硫化物製備於量子點敏化太陽能電池之光電極，並應用於水裂解反應，使之產生氫氣作為新型替代能源。以硝酸鋅、硝酸鎘、氧化硒及硫化鈉作為起始物，利用化學浸泡法(Chemical Bath Deposition, CBD) 於氧化錫參雜氟之導電玻璃(fluorine-doped tin oxide, FTO)表面上，製備不同層數量子點硫化物之光電極。當CBD循環層數為1、5及7時，運用紫外光-可見光吸收光譜儀與掃描式電子顯微鏡分別可觀察到光譜變化，與球狀、團簇狀，以及緞帶狀奈米材料之結構。另外以線性掃瞄伏安法測量光電流，在一個太陽光強度(100 mW cm-2)照射下，當電壓為1.3 V (vs. Hg/Hg2Cl2) 時， TiO2/(CdZnS)4/(CdZnSe)2/ZnS光電極之光電流可達 79.24 mA，可證明經CBD循環製成之量子點電極具有高電催化活性。此外將沉積不同量子點的光電極與硫化鈷反電極結合後製成不同的太陽能電池，在一個太陽光強度照射下測量其光電轉化效率，當使用的光電極為 TiO2/(CdZnS)4/(CdZnSe)2/ZnS 時，可得最大轉化效率η為 2.40 %。更進一步，以此光電極在定電壓下進行水裂解反應，由自製的氫氣收集器收集氫氣，可得其與白金對電極產氫率為 0.98 mmol/hr，以此可確定最佳化的光電極。

The purpose of this paper is to study the roles of formic acid and formaldehyde playing in the Direct Methanol Fuel Cells(DMFCs).The assumption is now widely accepted that the Oxidation-reduction intermediate of cell like formic acid and formaldehyde will hinder the reaction of DMFCs. At first, we recorded data which measured the efficiency of DMFCs working under the different temperature of fuel, then we recorded data which measured the efficiency of DMFCs working under the different consistency. In the end, we compared the data we recorded before and chose the best reaction environment as standard environment for the future experiment. Then we discover intermediate has positive effect on DMFCs. we separately put formic acid and formaldehyde into fuel, and we discover the efficiency is better than\r before. For example, the volt stability and volt intensity of DMFCs are better. The above conclusion is mainly based on open current volt, equally volt and electric current density which is the standard of evaluation.本實驗主要探討甲酸、甲醛等雜質在直接甲醇燃料電池中扮演的角色，一般認為甲酸等是甲醇在電池中反應的中間產物，大多數人認為這些中間產物會阻礙燃料電池的反應。而我們先針對了甲醇在各種溫度下電池的效能先做出了圖表，並使用不同濃度的甲醇燃料來測量電池的效能並與之前溫度的圖表做比較，選出最合適的直接甲醇燃料電池反應環境作為添加雜質實驗的標準環境。接下來我們在研究過程中發現，其實中間產物可能對電池有正面的效果，我們發現甲酸、甲醛等對直接甲醇燃料電池的電源輸出有正面的影響，例如電壓穩定性與電壓強度的增強。在研究中，我們將甲酸等加入燃料電池的燃料(甲醇)內，模擬甲醇因不當保存而產生的雜質，針對添加物的濃度做些調整，以電池的開路電壓(OCV)、平均輸出電壓、以及單位面積的電流密度作為評比電池效能的標準，並找出甲酸等對燃料電池效能的影響，並進一步找出最適合的電池燃料配置。

Based on environmental protection and new energy development, the energy containing low pollution and having high efficiency becomes more popular. The fuel cell is an emerging technology, which is the reason why it is considered as Green energy. However, high-price membrane electrode assembly (MEA) inhabits the development of fuel cell. Among these components in MEA, platinum-based electrode leads the most cost. We select the multi-walled carbon nanotubes (MWNTs) as catalyst support to improve electrode material performance and reduce Pt utilization. But the particle size and dispersion of platinum as well as character of catalyst support may significantly affect the efficiency of electrode.燃料電池因為具備低排放污染、低噪音及高轉換效率等環保特性，故被稱為綠色能源，可取代內燃機作為發電之能源系統。然而燃料電池中觸媒粒徑大小、分散情形以及使用不同的觸媒載體，均有可能會影響其電觸媒的催化效能，所以我們以「觸媒粒徑大小」、「觸媒分散情形」為主軸，著手以下的研究。本實驗在不同的酸鹼值下製備燃料電池的電極材料，並以電子顯微鏡等器材，觀察已披覆在電極上白金觸媒的特性，探討不同酸鹼環境對白金觸媒粒徑大小的影響，並探究白金觸媒粒徑大小與其發電效率的關係。

六種自行合成出來的聯吡啶釕錯合物Ru(bpy)₃、Ru(bpy)₂(phen) 、 Ru(bpy)₂dcbpy、Ru(phen)₃、Ru(phen)₂(bpy)、Ru(phen)₂dcbpy 及商用染料N3-dye，被成功的做成光敏性太陽能電池。光電流的產生率可由IPCE (incident photon-to-current conversion efficiency) 的測量可知。此類釕錯合物可以物理吸附或化學鍵結於TiO₂奈米粒子上。IPCE 的大小可以用來探討不同吸附方式的釕錯合物轉換光電流的效率。在物理吸附上Ru(phen)₂(bpy)的效率最好。化學鍵結的以N3 Dye 最好，我們合成的錯合物以Ru(bpy)₂dcbpy 較佳。此種以TiO₂奈米結構為承載基材的太陽能光電池(Dye-Sensitized Solar Cell)，染料仍以商用染料 N3-dye 最佳。本研究發現物理吸附的Ru complexes 也可產生光電流，若能最佳化，將可簡化染料錯合物之合成。 Six ruthenium complexes, Ru(bpy)₃, Ru(bpy)₂(phen), Ru(bpy)₂dcbpy, Ru(phen)₃, Ru(phen)₂(bpy), and Ru(phen)₂dcbpy were synthesized. These Ru complexes and N3 dye have been incorporated into the dye-sensitized solar cell system. The solar energy conversion of the ruthenium complexes were measured and converted to IPCE (incident photon-to-current conversion efficiency). There complexes were either chemically bonded or physically absorbed onto the nano-sized TiO₂ particles. The IPCE were utilized to compare the photon-to-current efficiency of these Ru complexes. Among the physical-absorbed dyes, Ru(phen)₂(bpy) has the highest IPCE. For chemical-absorbed dyes, the commercial N3 dye is still the best. Among the complexes synthesized in this research that are chemical-absorbed, Ru(phen)₂dcbpy has the highest IPCE The commercial N3 dye has the highest IPCE in the dye-sensitized TiO₂nanoparticle solar cell. We found that physically absorbed dye can convert photon to current. With better solar cell assembly, physically absorbed dye can have the same conversion efficiency as N3 dye.

In order to facilitate a paradigm shift from traditional high volume chemical experiments to an environmentally friendly microdose experiment; I had to innovate and overcome a lot of difficulties. After six generations of experiment design I successfully reduced the volume of the combined reactants to a single drop. I utilized many recycled components to build my apparatus including a vintage computer, a simple CD disk, optical sensors and a transistor from a common computer mouse. By using a CCD monitor with an external camera feed, the single drop chemical reaction can be observed in real time and a recording of the event can be made. I chose the focus of the experiment to be the reaction of sodium thiosulfate and hydrochloric acid to create a colloidal solution of sulfonium nanoparticles. By employing a custom-made transparency target to achieve a higher precision of measurement I have also conducted deeper research into the reaction order and the rate constants. 為了將傳統高劑量的化學實驗順利的推向顯微液滴的化學實驗上，今年我們更是創新突破了很多困難的關卡。 儀器設計由第一代減量研究到第六代的減量設計，目前已能成功的運用報廢的光碟片、報廢的電腦、報廢滑鼠內的感光二極體元件及電晶體來自製設計出兩反應物各一滴溶液做自動偵測反應的記錄。透過顯微鏡加裝的CCD電子螢幕目視觀看、拍成電子影片檔由電腦播放的目標。 因此，我選定了硫代硫酸鈉溶液和鹽酸溶液反應可產生硫奈米微粒的膠態溶液作為實驗的主軸及設計可較精確定量的投影片載液面，我們也企圖對其反應速率式的級數及反應速率常數做更深入的探討。

筆者利用自製的幾丁質與不同金屬的混合溶液而燒結出的奈米顆粒成效極佳，不但粒徑大小符合，在燒結的過程中也不需經過物理研磨及介面活性劑的輔助，並且在低溫下即可燒結，可以增加實用性以及商業價值。此外，在分解亞甲藍方面也有不錯的效率，並進一步從金屬氧化物之奈米膠體混合溶液比例的不同，決定其粗糙度（以AFM測定）及能隙改變，在陽光下有更高的應用效率。而在實驗的延伸研究上，希望應用在防菌、除污、甚至光電池。 We make use of self-made chitin with the mixed solutions of different metals to solder nano particles, and the result is excellent. The particle radius not only matches up to the size, but in the process of soldering nano particles, it doesn’t need any physical pulverizing or surfactant assistance. Also, it can solder in low temperature. And we could raise its practicality and the business value. What’s more, there is a good efficiency in decomposing Methylene Blue. We can further decide the roughness (measured with AFM) and the variation of the band gap from nano colloid of different metal oxide mixed ratios.Our experiment in the extending research aims to apply it to the defense of bacteria and pollution, and even photoelectric cell.