研究生: |
江麗芬 Chiang, Li Fen |
---|---|
論文名稱: |
銅修飾二氧化鈦光催化降解新興污染物之研究:以BPA及SMX為例 Copper modified-TiO2 photocatalysts for the degradation of BPA and SMX |
指導教授: |
董瑞安
Doong, Ruey An |
口試委員: |
盧明俊
白曛綾 盧重興 吳劍侯 王竹方 |
學位類別: |
博士 Doctor |
系所名稱: |
原子科學院 - 生醫工程與環境科學系 Department of Biomedical Engineering and Environmental Sciences |
論文出版年: | 2015 |
畢業學年度: | 103 |
語文別: | 英文 |
論文頁數: | 139 |
中文關鍵詞: | 銅修飾二氧化鈦 、磺胺甲噁唑 、雙酚A |
外文關鍵詞: | Cu-TiO2, SMX, BPA |
相關次數: | 點閱:3 下載:0 |
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銅修飾二氧化鈦為一新型環境淨化材料,其廣泛的被應用在光催化降解及氫能源還原的領域。在光催化降解部分,目前已有許多銅修飾二氧化鈦的合成方法,但因不同的方法所產生的銅物種的不同所造成的影響也不一樣,因此,系統性比較不同銅物種對二氧化鈦的影響為相當重要的課題。故本研究的主要目的是嘗試利用微波輔助浸滲(microwave-assisted impregnation)合成Cu2+-TiO2,高溫熱處理(high temperature heating)合成CuO-TiO2及化學還原(chemical reduction)合成Cu0-TiO2且利用雙酚A(BPA)及磺胺甲噁唑(SMX)來進行銅修飾二氧化鈦之光催化效能評估。
在Cu2+-TiO2部分,主要是利用微波輔助浸滲法來合成0.006-0.065 wt% Cu2+-P25和0.012-0.072 wt% Cu2+-ST01。Cu2+-TiO2主要是由二價的CuO修飾在二氧化鈦上。而Cu2+-TiO2中的Cu2+提供一個能階,故能縮短其電子跳躍的距離且降低電子電洞再結合的能力而有效的提升其可見光催化效能。在SMX的可見光催化降解部分,Cu2+-P25的反應速率為P25的2.9-14倍且0.045 wt% Cu2+-P25具有最佳的光催化效能。在BPA的可見光催化降解部分,Cu2+-P25的反應速率為P25的1.5-2.3倍且0.039 wt% Cu2+-P25具有最佳的光催化效能。而Cu2+-ST01的反應速率為ST01的1.5-3.7倍且0.055 wt% Cu2+-ST01具有最佳的光催化效能。
在CuO-TiO2部分,主要是利用高溫熱處理法來合成1.1-22.4 wt% CuO-TiO2奈米棒。CuO-TiO2奈米棒主要是由二價的CuO和Cu(OH)2修飾在二氧化鈦上。而CuO -TiO2奈米棒中的CuO提供一個儲存電子的位置,故能降低TiO2電子電洞再結合的能力而有效的提升其紫外光催化效能。在BPA的紫外光催化降解部分,CuO-TiO2奈米棒的反應速率為TiO2奈米棒的0.5-5.5倍。
在Cu0-TiO2部分,主要是利用化學還原法來合成0.4-20.0 wt% Cu0-TiO2奈米棒。Cu0-TiO2奈米棒主要是由Cu2O和Cu0修飾在二氧化鈦上。而Cu0-TiO2奈米棒中的Cu0提供一個儲存電子的位置,故能降低二氧化鈦電子電洞再結合的能力而有效的提升其紫外光催化效能。在可見光狀況下,可見光激發Cu2O產生光電子且經由Cu0到TiO2,故能在可見光下進行光催化反應且降低電子電洞再結合的能力而有效的提升其光催化效能。在BPA的紫外光催化降解部分,Cu0-TiO2奈米棒的反應速率為TiO2奈米棒的1.3-18.4倍且6.9 wt% Cu0-TiO2奈米棒具有最佳的光催化效能。在BPA的可見光催化降解部分,Cu0-TiO2奈米棒的反應速率為TiO2奈米棒的反應速率分別為P25跟Cu-P25的6跟5倍。
本研究結果顯示銅修飾TiO2催化劑能有效率被紫外光跟可見光激發來降解BPA跟SMX且銅修飾TiO2也極具潛力來降解其他新興汙染物。
Copper-based TiO2 have been demonstrated to be a potential photocatalyst for
photodegradation and hydrogen production. In the photodegradation area, many
method had been used to synthesize different Cu species-TiO2, which caused different
effects in the photodegradation. Therefore, a systematic comparison for different Cu
species on TiO2 is needed. The main purpose of this study is to use
microwave-assisted impregnation, high temperature heating and chemical reduction to
synthesize Cu2+-TiO2, CuO-TiO2 and Cu0-TiO2, respectively. Bisphenol A (BPA) and
sulfamethoxazole (SMX) were used as target compounds to evaluate the
photodegradation efficiency and rate of different Cu species-TiO2.
Cu2+-TiO2 was synthesized by microwave-assisted impregnation. The mass
loadings of Cu(II) were 0.006-0.065 wt% copper for P25 and 0.012-0.072 wt% copper
for ST01 and the major species of copper was CuO on the Cu-P25. Due to the redox
potential of Cu(II)/Cu(I) (0.3-0.5 V vs. SHE) and copper oxide as an electron
mediator, Cu2+-TiO2 have the potential to enable the absorption of light not only in the
ultraviolet but also in the visible light wavelength region and reduce the e/h
recombination to improve the photocatalytic efficiency. The pseudo-first-order rate
constants (kobs) for SMX photodegradation by Cu2+-P25 were 2.9–14.1 times higher
than that of pure Degussa P25 and the relative activity of Cu2+-P25 for BPA
photodegradation was 1.5-2.3 times. The relative activity of Cu2+-ST01 for BPA
photodegradation was 1.5-3.7 times. The optimal loading of Cu(II) to enhance the
photocatalytic activity of P25 and ST01 were 0.045 wt% and 0.055 wt%, respectively.
CuO-TiO2 nanorods were synthesized by high temperature heating and
CuO-TiO2 nanorods contain 1.1-22.4 wt% copper with CuO and Cu(OH)2 on
CuO-TiO2. CuO on the CuO-TiO2 nanorods was as an electron tank to reduce the e/h
recombination and improve the photocatalytic efficiency under the UV light
irradiation. BPA were used to evaluate the photodegradation efficiency and rate of
Cu-TiO2 nanorods under the irradiation of 365 nm UV light. The relative activity of
CuO-TiO2 nanorods were 0.5-5.5 times.
Cu0-TiO2 nanorods with 0.4-20.0 wt% copper were synthesized by chemical
reduction. The XRD and XPS results indicated that Cu species on the Cu-TiO2
nanorods were mainly Cu2O and Cu0. Cu0 as an electron tank on the Cu0-TiO2
nanorods reduce the e/h recombination and improve the photocatalytic efficiency
under the UV light irradiation. Cu2O was a semiconductor to excite by visible light
and produce electron to Cu0 and TiO2 to improve the photocatalytic efficiency. The
Cu0-TiO2 nanorods exhibited excellent photocatalytic activity towards BPA
photodegradation. The relative activity of Cu0-TiO2 nanorods were 1.3-18.4 times and
the optimal loading of Cu to enhance the photocatalytic activity of TiO2 nanorods
were 6.9 wt%. In addition, the kobs for BPA photodegradation by 6.9 wt% Cu0-TiO2
nanorods increases by factors of 6 for P25 and 5 for Cu0-P25 in the presence of 460
40 nm visible light.
Results obtained in this study clearly demonstrate that Cu modified-TiO2
nanomaterials are an effective photocatalyst for degradation of BPA and SMX under
UV or visible light conditions and have potential to decompose emerging pollutants.
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