- 學位論文
應用於水裂解反應產氫之高性能 Ru/(CuIn)xZn2(1-x)S2光觸媒研究
High-Performanced Ru/(CuIn)xZn2(1-x)S2 Photocatalysts for Water-splitting Reaction to Produce Hydrogen
摘要
本研究在探討可見光水裂解反應產氫之Ru/(CuIn)xZn2(1-x)S2光觸媒的製備與應用。在本研究中，光觸媒的製備是以不同比例之Cu2S、In2S3與ZnS先混合作為前驅物，將助熔劑Na2Sx加入前驅物，利用熔鹽法(flux Method) 以1℃/ min升溫速度升溫至觸媒之製備溫度並保持恆溫1小時。所得產物再經水洗、過濾而得(CuIn)xZn2(1-x)S2光觸媒；再將Ru負載在(CuIn)xZn2(1-x)S2光觸媒上即得Ru/(CuIn)xZn2(1-x)S2光觸媒。光觸媒之性質分別以X-ray繞射儀 (XRD)、Uv-Vis光譜儀、掃描式電子顯微鏡(SEM)、能量散佈光譜儀(EDS)等進行分析。由XRD結果得知觸媒之製備溫度為600℃所得之光觸媒為最佳混合物晶體結構。由Uv-Vis可知以ZnS:CuInS2不同比例會造成臨界波長的平移，隨著CuInS2含量增加造成臨界波長紅平移，當觸媒為(CuIn)0.14Zn1.72S2時可得最適水裂解產氫之臨界波長。由SEM結果得知光觸媒顆粒隨反應溫度增加而變大，另外在製備溫度600℃下比較不同ZnS-CuInS2混合比例光觸媒結果其粉末顆粒隨著CuInS2含量增加而變大。由EDS鑑定結果得知光觸媒成分為(CuIn)xZn2(1-x)S2。光觸媒之水裂解產氫反應是在加入Na2S(0.25M)/K2SO3(0.35M)犧牲劑之批式反應器中以450W金屬鹵素燈照射下進行。由實驗結果得知，以600℃製備之Ru(0.5wt%) /(CuIn)0.14Zn1.72S2光觸媒之水裂解反應活性最佳，其產氫速率可達到967.9μmole/h。
並列摘要
In this study, the preparation and application of photocatalysts Ru/(CuIn)xZn2(1-x)S2 for hydrogen production via visible light illuminating water-splitting reaction were investigated. The photocatalysts were prepared with the precursors containing Cu2S, In2S3 and ZnS with different proportions. The flux method was proceeded by adding the flux Na2Sx into precursors to rise the temperatures at the rising rate of 1℃/min to different reaction temperatures and maintained for 1 hour. The photocatalysts (CuIn)xZn2(1-x)S2 were obtained after washing with the distilled water and filtration. The prepared photocatalysts (CuIn)xZn2(1-x)S2 were then loaded with Ru to obtain the photocatalysts Ru/(CuIn)xZn2(1-x)S2. The photocatalytic characterization, were analyzed by means of X-ray diffraction (XRD), Uv-Vis spectrophotometer (Uv-Vis), scanning electronic microscope (SEM) and energy dispersive spectrometer (EDS). It could be seen from XRD results that the photocatalysts prepared at the reaction temperature of 600℃, possess the best crystalline structure. From Uv-Vis results, it could be seen that the variations of CuInS2:ZnS proportions in prepared photocatalysts all caused the absorption edges to shift, especially the red shift increased with the increasing of CuInS2. It could be found from the results of water-splitting reaction that the (CuIn)0.14Zn1.72S2 possess optimal absorption edges for photocatalytic hydrogen production. From SEM results, the particle sizes of the photocatalysts increased with the increase of preparation temperatures. On the other hand, by the observation of photocatalysts prepared with various ZnS-CuInS2 proportions under 600℃ calcination, it could be seen that the particle sizes increased with the increase of CuInS2 proportion. Finally, the composition of (CuIn)xZn2(1-x)S2 was identified through EDS results. The photocatalystic water-splitting reaction for hydrogen production was carried out in a batch reactor under the irradiation of the 450W metal halide lamp with the addition of sacrificial reagent Na2S(0.25M)/K2SO3(0.35M). From the experimental results, the optimal hydrogen production rate could reach to 967.9μmole/h with Ru(0.5wt%)/ (CuIn)0.14Zn1.72S2 prepared at 600℃.
參考文獻
延伸閱讀
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