由於鈀金屬對二氧化碳電化學還原反應具有獨特的催化能力，本研究使用鈀奈米粒子/碳黑觸媒 (Pd/XC72) 塗佈之氣體擴散電極與旋轉盤環電極進行二氧化碳電化學還原反應的研究。利用電化學分析來探討在還原反應進行中，鈀金屬上之氫吸脫附的電化學反應變化，以及其對二氧化碳還原催化能力的影響。在第4章節中確認一氧化碳是反應的主要產物之一，並且發現PdHx的α和β吸收相位量，會受到一氧化碳吸附於鈀奈米粒子上 (Pd NPs) 活性位的影響而減少。此外，在較正的施加電位範圍中，當大多數吸附於Pd/XC72活性位上的一氧化碳被去除時，觸媒對於氫氣產生反應以及二氧化碳電化學還原反應的活性會被大幅活化，顯示在此過電位範圍中，還原反應的速率受到一氧化碳脫附速率的限制。
在第5章節中，本文藉由在氣體擴散電極與旋轉盤環電極上進行電化學分析，證明Pd/XC72的選擇性會受到鈀表面的氫吸附覆蓋率的影響。當Pd/XC72上的氫吸附覆蓋率低於約0.2時，二氧化碳還原反應的主要產物會從甲酸轉變成一氧化碳。本研究更進一步發現可能是羧基中間體 (COOH*) 在白金環狀電極上的氧化訊號峰，是為此中間體存在於二氧化碳電化學還原反應中的重要證據。
最後，在第6章節中，本研究開發出修飾鈀表面的新製程。藉由在醋酸溶液中加熱迴流的處理方式，Pd/XC72的一氧化碳自我毒化速率會被大幅地降低。此外本研究發現在紫外-可見光譜中，可以觀察到醋酸根離子吸附於鈀金屬表面、生成類似醋酸鈀鹽類所產生的吸收光訊號，並認為這些物質在鈀金屬表面的溶解與再沉積，會使得鈀金屬表面上具有較高一氧化碳生成速率的邊緣/角活性位的數量下降。其結果使得經醋酸處理的Pd/XC72的甲酸產生電量為原本的4倍，顯示此種製程可以顯著提升Pd/XC72對於二氧化碳還原產生甲酸的選擇性與催化能力。

Due to the unique catalytic ability of electrochemical reduction reaction of carbon dioxide (CO2ER) on palladium, the palladium nanoparticles/carbon black (Pd/XC72) is studied on gas diffusion electrodes (GDE) and rotating ring disk electrode (RRDE). This work discusses the change in adsorption/absorption responses of hydrogen on palladium during CO2ER and its effects on the catalytic ability and selectivity of palladium for the CO2ER with electrochemical analysis. In chapter 4, carbon monoxide (CO) is confirmed to be one of the main products of CO2ER on Pd/XC72. The adsorption of CO on the active sites of the palladium nanoparticles (Pd NPs) is found to reduce the amounts of PdHx in the α and β phases. Also, the activities of Pd/XC72 for both hydrogen evolution reaction (HER) and CO2ER within less negative potential range were greatly regenerated when most of adsorbed CO molecules on active sites were removed, which showed that the CO2ER rate was limited by the desorption rate of CO in the less negative potential region.
In chapter 5, the selectivity of Pd/XC72 is proved to be dependent on the coverage of H adsorption (Hads) from the electrochemical analyses through the usage of both GDE and RRDE. The main product of CO2ER on Pd/XC72 is changed from formate to CO when the coverage of Hads is lower than ca. 0.2. In addition, in the RRDE analyses, a peak corresponding to the oxidation of carboxyl intermediate (COOH*) on the platinum ring electrode is found, which is also a strong evidence for the existence of COOH* intermediate during the CO2ER.
Finally, in chapter 6, a new way was developed to modify the surface of Pd NPs. By refluxing treatment in acetic acid, the rate of CO self-poisoning on Pd/XC72 was significantly reduced. Moreover, the adsorption of acetates onto the surface of Pd to form the Pdx(OAc)2x-like species during the refluxing in glacial acetic acid is observed in UV-vis spectra. The dissolution and re-deposition of these species are considered to be responsible for the changes in the morphology of Pd and the decrease in the amount of edge/corner sites, which have higher rates of CO production. As a result, the charge of formate formation on Pd/XC72 is about 4 times after this acetic acid treatment, showing that the selectivity and activity of the CO2ER to formate on Pd/XC72 are enhanced obviously.

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