Clean Technology (청정기술)

The Korean Society of Clean Technology (한국청정기술학회)
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Comparative Studies on Mechanism of Photocatalytic Degradation of Rhodamine B with Sulfide Catalysts under Visible Light Irradiation

가시광선하에서 황화물계 광촉매를 이용한 로다민 B의 광분해 반응기구에 대한 비교 연구

  • 이승현 (부경대학교 공과대학 공업화학과) ;
  • 정영재 (부경대학교 공과대학 공업화학과) ;
  • 이종민 (부경대학교 공과대학 공업화학과) ;
  • 김대성 (부경대학교 공과대학 공업화학과) ;
  • 배은지 (부경대학교 공과대학 공업화학과) ;
  • 홍성수 (부경대학교 공과대학 화학공학과) ;
  • 이근대 (부경대학교 공과대학 공업화학과)
  • Received : 2019.01.22
  • Accepted : 2019.02.22
  • Published : 2019.03.30
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Abstract

CdS and CdZnS/ZnO materials were prepared using precipitation method and used as photocatalysts for the photocatalytic degradation of rhodamine B (RhB) under visible light irradiation. The prepared photocatalysts were also characterized by XRD and UV-vis DRS. The results indicated that the photocatalysts with intended crystalline structures were successfully obtained and both the CdS and CdZnS/ZnO can absorb visible light as well as UV. The photocatalytic activities were examined with the addition of scavenger for various active chemical species and the difference of reaction mechanisms over the catalysts were discussed. The $CH_3OH$, KI and p-benzoquinone were used as scavengers for ${\cdot}OH$ radical, photogenerated positive hole and ${\cdot}O_2{^-}$ radical, respectively. The CdS and CdZnS/ZnO showed different photocatalytic degradation mechanisms of RhB. It can be postulated that ${\cdot}O_2{^-}$ radical is the main active species for the reaction over CdS photocatalyst, while the photogenerated positive hole for CdZnS/ZnO photocatalyst. As a result, the predominant reaction pathways over CdS and CdZnS/ZnO photocatalysts were found to be the dealkylation of chromophore skeleton and the cleavage of the conjugated chromophore structure, respectively. The above results may be mainly ascribed to the difference of band edge potential of conduction and valence bands in CdS, CdZnS and ZnO semiconductors and the redox potentials for formation of active chemical species.

CdS 및 CdZnS/ZnO를 침전법으로 제조하여 가시광선하에서의 로다민 B의 광분해 반응에 대한 광촉매로 이용하였다. 제조된 광촉매들은 X선 회절분석기와 UV-vis 확산반사 분광법 등으로 특성을 분석하였으며, 그 결과 원하는 결정구조를 지닌 광촉매들이 생성되었으며 또한 CdS 및 CdZnS/ZnO 두 가지 광촉매 모두 자외선뿐만 아니라 가시광선 영역의 빛도 효율적으로 흡수함을 알 수 있었다. 여러 종류의 활성 화학종에 대한 포집제들을 첨가하면서 각각의 광촉매에 대한 활성을 조사하였으며, 특히 두 가지 촉매상에서의 반응기구 차이점에 중점을 두고 고찰하였다. 이때 $CH_3OH$, KI 및 p-benzoquinone을 각각 ${\cdot}OH$ 라디칼, 광여기 정공 그리고 ${\cdot}O_2{^-}$ 라디칼에 대한 포집제로 이용하였다. 각각의 광촉매상에서는 서로 다른 반응기구에 의해서 반응이 진행되는 것으로 나타났다. CdS 광촉매 반응에서는 ${\cdot}O_2{^-}$ 라디칼이 그리고 CdZnS/ZnO 광촉매 반응에 있어서는 광여기 정공이 중요한 역할을 하는 것으로 판단되며, 따라서 CdS와 CdZnS/ZnO 각각의 광촉매상에서는 발색단 골격의 탈알킬화 반응 및 발색단 콘쥬케이트 구조의 절단 과정을 통하여 반응이 우선적으로 진행된다는 것을 알 수 있었다. 이러한 결과들은 CdS, CdZnS 그리고 ZnO 각각 반도체들의 전도대와 가전자대의 띠끝 전위와 활성 화학종 생성에 대한 산화환원 전위의 차이에 주로 기인한 것으로 생각된다.

Keywords

CJGSB2_2019_v25n1_46_f0001.png 이미지

Figure 1. XRD patterns of CdS and CdZnS/ZnO catalysts.

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Figure 2. UV-vis DRS of CdS and CdZnS/ZnO catalysts.

CJGSB2_2019_v25n1_46_f0003.png 이미지

Figure 3. UV-vis spectral change of rhodamine B (RhB) solution in the presence of photocatalyst (a) CdS and (b) CdZnS/ZnO under visible light irradiation.

CJGSB2_2019_v25n1_46_f0004.png 이미지

Figure 4. Effect of scavenger on the photocatalytic degradation of rhodamine B in the presence of photocatlyst (a) CdS and (b) CdZnS/ZnO under visible light irradiation.

CJGSB2_2019_v25n1_46_f0005.png 이미지

Figure 5. UV-vis spectral changes during photocatalytic degradation of RhB using CdS photocatalyst in the presence of sca-venger (a) CH3OH, (b) KI, and (c) p-benzoquinone.

CJGSB2_2019_v25n1_46_f0006.png 이미지

Figure 6. UV-vis spectral changes during photocatalytic degradation of RhB using CdZnS/ZnO photocatalyst in the presence of scavenger (a) CH3OH, (b) KI, and (c) p-benzoquinone.

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