二氧化錳作為一種環境友好，地殼豐度高的材料，越來越引起研究者的注意，在超級電容、電容去離子等應用中，二氧化錳基奈米材料顯示出高理論電容值。但對於二氧化錳表面特性，如表面電荷等影響的研究較少。因此本論文以二氧化錳基奈米材料為對象，通過其在環境技術中的電容去離子效率為評價，對結構、表面電荷、孔徑影響等問題進行探討。
通過以活性炭為載體的不同晶相二氧化錳(α,β,γ,和 δ)在電容去離子效率的比較和酸堿滴定分析，發現由於二氧化錳奈米材料晶相結構引起的表面異質性，導致表面羥基去質子化，因此去離子效率隨著表面負電荷增加而降低。而交流阻抗分析顯示，高表面電荷會誘導擴散層電阻增加，抑制共離子的進入，因此施加的偏壓被用於客服電雙層阻力，而非電吸附，導致去離子效率降低。
為進一步討論二氧化錳本身表面電化學對電容去離子影響，摻雜鐵、鈷和鎳離子的α-二氧化錳奈米材料被用於電容去離子陰極。結果同樣顯示，去離子效率隨表面負電荷密度增加而降低，與碳基材料微孔特性不同，二氧化錳奈米材料為介孔環境，在介孔中高離子化表面發生了明顯的共離子排斥效應。而通過摻雜技術調整結構應力，進而調控表面電荷，將其與微孔改性相結合，將有效提升去離子效率。
為深入了解二氧化錳基奈米材料的電化學及微孔碳基材料的電容特性對去離子效率影響，製備摻雜不同比例二氧化錳的電容去離子電極，對其在三個連續充放電循環中施加不同偏壓下的CDI性能進行評價，採用三種不同方式進行電容估算：1）CV曲線面積 2）定電流除以偏壓 3）放電尖峰電流（電極表面累積電荷）除以偏壓。研究結果表明，從3）中得出的電容與除鹽效率之間存在線性關係，電容隨交換電流的增加而增大。表明，碳質基質的微孔和高導電性分別是發展雙電層和達到高交換電流的重要因素；另一方面，具有高交換電流電極的電化學特性對電荷積累和所產生的高除鹽效率非常重要。
最後，採用竹炭（微孔碳基）為基質，製備磁性竹炭-二氧化錳復合材料，活化過硫酸鹽降解染料.結果顯示，磁性有利於後端竹炭的收集和活化，該復合材料具有吸附及催化雙效作用，硫酸根自由基是主導自由基。

As an environmentally friendly, nature abundant material, manganese dioxide attracts more attention in environmental technique and energy storage. In addition, MnO2 shows excellent theoretical specific capacitance by the applied in supercapacitor and capacitive deionization. However, there is seldom study to explore the effect of surface property, such as surface charge. So in this thesis, we focus on MnO2 and investigate the effect of structure, surface charge and pore size by evaluation with capacitive deionization performance.
To studying the correlation between the CDI performance and MnO2 structure, a series of MnO2 (α,β,γ,and δ phase) were synthesized and supported on activated carbon as cathodes in simple batch mode experiments. Results of alkalimetric-acidimetric titration revealed that due to surface heterogeneity originating from the structure of MnO2 phase, the deionization efficiency decreased with increase in the negative surface charge as a result of deprotonated surface hydroxyl groups. The electrochemical impedance spectroscopy analyses indicated highly charged surface and conversely inhibited the access of co-ions in the CDI process. In this case, the applied bias mainly allowed ions overcome the double layer resistance, instead of accumulation (electrosorption) on the electrode.
To explore how the surface chemistry of MnO_2 itself influences CDI efficiency, A series of Fe, Co, and Ni-doped α-MnO_2 (< 0.1 mol%) was used as a model cathode material in CDI. The results show also, that CDI efficiency decreased with increasing negative surface charge density. It likely attributed to the appreciable co-ion expulsion occurring at highly ionized surface in the mesopores of MnO_2. It is thus concluded that the combination of structural stress adjustment with doping elements to modified the surface charge and a microporous environment would be important for CDI efficiency enhancement by minimizing the co-ion exclusion effect.
To deep understanding the interplay between the electrochemical behavior of associated manganese oxide (MnO2) and the capacitive property of microporous carbonaceous support is essential for further capacitive deionization (CDI) performance enhancement. A series of electrodes with different MnO2/carbon weight ratios were thus fabricated and their CDI performances at different applied potentials in three consecutive charging/discharging cycles were evaluated. The capacitance of these electrodes was estimated through three distinct routes: 1) the area under CV curves, 2) the current passing through the electrodes in the given charging time intervel and then divided by the applied voltage (C=Q/V= (i × t )/V ), and 3) the area under the discharge spike current (accumulated charges at electrode surface then divided by the applied voltage). Interestingly, a rather linear correlation between the capacitacne derived from 3) and salt removal/released was noted and this linear correlation was capable of accounting for all the salt removal behavors in the examined voltage window. By further arranging obtained CV curves in a manner similar to the Tafel plot, it was found that the capacitacne derived from 3) increased with increasing exchange current. Based on these experimental observations, it was thus concluded that the micropores and high electric conducitity of the carbonaceous support is important for electic double layer capacitance development and for reaching a high exchange current, respectively. On the other hand, an electrochemical property of an electrode being capable of possessing high exchange current is important for charge accumulation and consequently high salt removal by a CDI cell.
Finally, Bamboos based activated carbon (BAC) were synthesis with magnetic nanoparticle and Mn-ions to form a Mn@MBAC nanocomposite, the magnetic property benefits the collection and regeneration in the post-process. The as-synthesized nanocomposites used as bifunctional materials for the adsorption and catalytic oxidation of azo dye methyl orange degradation. The results demonstrated that the added magnetic nanoparticle and Mn-ions significantly affected the elemental composition, leading to improved adsorption efficiency as well as the catalytic activity . The data fit well with the Freundlich isotherm model and pseudo-second-order kinetic model. Racial scavenging experiments indicated that the SO4·- was the primary radical.

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