2021/12/22 Group Meeting
Elliot
裝填顆粒污泥碳光電催化劑的三維光電催化反應器
的開發用於高效廢水處理
• 隨著社會的發展，大量的污染物，如染料、抗生素和殺蟲劑被釋放到水環境中。
而傳統的生物廢水處理技術處理這些頑固化合物的能力是有限的。
• 高級氧化程序(AOP) 可有效降解難降解的污染物，並且已應用各種 AOP 組合於
高級廢水處理
• With the development of society, massive amounts of pollutants, such as dyes,
antibiotics and pesticides are released into water environments.
Traditional biological wastewater treatment technologies present limited
capability of dealing with these recalcitrant compounds . Advanced oxidation
processes (AOPs) are efficient to degrade refractory pollutants, and various
AOPs have been combined for advanced wastewater treatment
• 作為一種典型的AOPs，光催化(PC) 是一種高效的、非能源密集型的分解頑固化合物的方法。TiO 2和 ZnO等半導體被廣泛用作光
催化劑。電子（e -）和空穴（h +）在紫外線或可見光照射下產生，進一步攻擊污染物分子。然而，半導體光催化劑產生的電荷很
容易複合，降低了PC的效率。並且降解中間體的毒性往往高於PC後的初始化合物。
•
因此，一些研究人員嘗試通過施加外部電場將電催化（EC）結合到 PC 中。
• EC也屬於AOPs，可以有效礦化污染物. 污染物可以在陽極直接氧化，也可以被反應體系中存在的活性氧間接攻擊。儘管EC具有通
用性和環保性等優點，但EC的高能耗和電極材料的使用壽命有限，阻礙了進一步的環境應用
•
photocatalysis (PC) is an efficient, non-energy intensive method of decomposing recalcitrant compounds . The semiconductors
such as TiO2 and ZnO are widely utilized as the photocatalysts. The electrons (e−) and holes (h+) are generated under ultraviolet
or visible light irradiation, further attacking the pollutant molecules . However, the generated charges of semiconductor
photocatalysts are readily to recombine, lowering the efficiency of PC . And the toxicity of degradation intermediates is often
higher than their parent compounds after PC . Therefore, some researchers try to incorporate electrocatalysis (EC) into PC by
applying external electric field. EC also belongs to AOPs, which can effectively mineralize the pollutants The pollutants can be
directly oxidized at the anode, or be indirectly attacked by reactive oxygen species existing in the reaction system . In spite of the
advantages of versatile and environmental friendly of EC, the high energy consumption of EC and the limited life time of
electrode materials imped further environmental applications
• 光電催化（PEC）通過整合 PC 和 EC 的優勢而引起了廣泛的興趣。一些研究人員利用光催化劑作為EC的陽極，在光陽極上施加
電位，驅使光生電子遠離空穴，產生更多的活性物質來處理廢水。在這個 PEC 過程中，EC 降解的污染物通常被忽略，因為施加
在光陽極上的偏壓較低。
• 自 1972 年以來，TiO 2已成功應用於在紫外光下光電化學水分解以產生 H 2。而且截至目前為止已經做了大量研究來提高光催化劑
的性能。
• 然而，在另一個 PEC 系統中，EC 可以對污染物降解做出主要貢獻。開發了一種光輔助電化學系統，其陽極同時具有優異的 PC
和 EC 性能。光照射會迅速氧化沉積在陽極表面上的中間體，延遲電極鈍化並抑制中間體的積累。因此，與 PC 或 EC 相比，PEC
是一種很讚的難降解廢水淨化方法。
• Recently, photoelectrocatalysis (PEC) has attracted wide interests by integrating the superiorities of PC and EC. Some
researchers utilize photocatalysts as the anode of EC and apply potential on the photoanode to drive the photogenerated
electrons away from the holes, producing more active species to treat wastewater . In this PEC process, the pollutants degraded
by EC are usually ignored because of the low bias applied on photoanode . However, in another PEC system, EC can make
primary contributions to pollutants degradation. A photo assisted electrochemical system has been developed, whose anode has
both excellent PC and EC properties. The light irradiation rapidly oxidizes the intermediates deposited on the anodic surface ,
deferring electrode passivation and inhibiting the accumulation of intermediates. Thus, PEC is an impressive approach to
purifying the refractory wastewater compared to PC or EC.
• 電極在 PEC 程序中是相當關鍵的部分。固定有光催化劑的薄膜電極具較高的光電活性，有利於光催化劑從處理過的廢水中分離。
然而，由於薄膜電極的光電流低，產生的活性氧種類有限。進水的有機負荷通常要求較低，需較長的水解停留時間才能完全降解
• 此外，由薄膜電極構成的二維（2D）電極系統在實際應用中具有一定的缺點，像是傳質限制、時空產率小和面積體積比低
• 因此有人提出了三維 (3D) 電極系統，通過在兩個對電極之間填充粒子電極來克服 2D 電極系統的局限性。粒子電極的存在顯著增
強了傳質，並且這些粒子的大比表面積提供了更多的反應位點。
• The electrode plays a critical role in the PEC process. The thin-film electrode immobilized with photocatalysts has high
photoelectric activity and facilitates the separation of photocatalysts from the treated wastewater . However, limited amounts of
reactive oxygen species are generated due to the low photocurrent of the thin-film electrode . The organic loads of influent are
usually required to be low, and long hydrolytic retention time is needed to achieved complete degradation . In addition, the thinfilm electrode constituted two-dimensional (2D) electrode system has intrinsic drawbacks in practical application, such as mass
transfer limitation, small space–time yield, and low area-volume ratio . Three-dimensional (3D) electrode system is proposed to
overcome the limitations of 2D electrode system by filling particle electrodes between two counter electrodes. The presence of
particle electrodes significantly enhances the mass transfer, and the large specific surface area of these particles provides more
reactive sites.
• 安學者等人。通過將光源和懸浮的TiO 2引入顆粒活性炭（GAC）填充的電化學反應器中，首次發明了3D光
電催化反應器（3D-PER）
• 最近，各種異相光催化劑如 TiO 2、Ag 2 O、ZnO、SnO 2和 ZrO 2被用於 3D-PER 以提高光催化功能。通常，
這些光催化劑負載在導電介質上，例如 GAC 以傳導 EC 以及提高分離性能。將光催化氧化與 3D 電化學技術
相結合的 3D-PER 在處理不透明的染料廢水方面顯示出潛勢
• An et al. invent a 3D photoelectrocatalytic reactor (3D-PER) for the first time by introducing the light source
and suspended TiO2 into a granular activated carbon (GAC) packed electrochemical reactor . Lately,
various heterogeneous photocatalysts such as TiO2, Ag2O, ZnO, SnO2, and ZrO2 are utilized in the 3D-PER
to improve the photocatalytic function . Usually, these photocatalysts are loaded on the conductive medium,
e.g. GAC to conduct EC as well as to improve the separation performance . The 3D-PER which combines
photocatalytic oxidation with 3D electrochemical technology shows great potential in the treatment of
opaque dye wastewater
• 之前的研究中，這種顆粒污泥碳 (GSC)超棒的光催化材料被製造出來，並在 3D 電化學反應器中
作為顆粒電極顯示出突出的性能，由於GSCs的分級孔結構和優異的電催化性能的結合，所以廢水
處理效率保持穩定。
• 所以此篇paper中，通過填充 GSCs 光電催化劑開發了一種新型 3D-PER，並應用於降解模擬羅丹
明 B (RhB) 廢水。
• In our previous study, the granular sludge carbons (GSCs) were fabricated and showed
prominent performance in 3D electrochemical reactor as particle electrodes . The wastewater
treatment efficiency maintained stable due to the joint of hierarchical-pore structure and excellent
electrocatalytic property of GSCs . We also found that GSCs are enriched in ZnO component
originating from ZnCl2 activation during fabrication, that was an excellent photocatalytic material.
Herein, a novel 3D-PER was developed by packing GSCs photoelectrocatalysts, and applied to
degrade simulated Rhodamine B (RhB) wastewater.
Fig S1、The photographs of the GSCs
Solid實心的
Hollow空心的
Fig. 1. Schematic diagram of the 3D-PER.
圖1。3D-PER 的示意圖
Fig S2、The evolutions of current (a) and power (b) for the 3D-PERs filled with GSC and GSC15 during EC and PEC processes
在 EC 和 PEC 過程中的電流（a）和功率（b）的變化情況（填充 GSC 和 GSC-15 的 3D-PER）
Fig. 2. Removal efficiency of RhB using (a) GSC and
(b) GSC-15 in the 3D-PER for the first cycle; pseudofirst-order kinetics for RhB degradation in 3D-PER fill
with (c) GSC, and (d) GSC-15 for the first cycle; RhB
removal efficiency in 3D-PER fill with (e) GSC and (f)
GSC-15 during continuous operation of 11 cycles.
圖2。去除 RhB 的效率使用 (a) GSC 和 (b) GSC-15
(3D-PER 填充)在第一個循環的 3D-PER 中（c）GSC
和（d）GSC-15 用於第一個循環中 RhB 降解的偽一級
動力學；在 11 個循環的連續操作期間(3D-PER 填充)
（e）GSC 和（f）GSC-15 中的 RhB 去除效率
Fig S3、Nitrogen adsorption-desorption isotherms of the GSCs
GSC的氮氣吸附-脫附曲線等溫線
GSCs在RhB降解方面表現出
良好的性能，特別是在AD過
程中。GSCs 的多孔結構在
去除 RhB 中發揮了重要作用。
GSCs的氮吸附-解吸等溫線
（圖S3 ）屬於IV型，顯示了
介孔材料的特性。
Fig. 3. Porous distribution of the GSCs in terms of micropores and mesopores (a), and
macropores (b); SEM images of GSC (c) and GSC-15 (d); XRD patterns of GSC and GSC-15
(e); XPS spectrum of GSC and GSC-15 (f); high resolution XPS spectrum of Zn 2p (g) and Fe
2p (h) of the GSCs.
圖3。GSC 在微孔和中孔 (a) 和大孔 (b) 方面的多孔分佈；GSC (c) 和 GSC-15 (d) 的 SEM 圖像；
GSC和GSC-15(e)的XRD圖譜；GSC 和 GSC-15 (f) 的 XPS 光譜；GSC 的 Zn 2p (g) 和 Fe 2p
(h) 的高分辨率 XPS 光譜。
Fig. 4. CVs of the GSCs recorded in
5 mM K4Fe(CN)6 + 0.1 M KCl solution at
0.1 V/s scan rate (a); UV–vis absorption
spectra of the GSCs (inset: bandgap
evaluation from Tauc plots)
(b); EIS Nyquist plots of the GSCs in
5 mM K3Fe(CN)6 + 0.1 M KCl solution,
with 0.01–106 Hz frequency and 5 mV
amplitude (inset: Nyquist plots at the
high frequency) (c); I-t curves of the
GSCs in 0.1 M Na2SO4 electrolyte (d).
圖 4。在 5 mM K 4 Fe(CN) 6 + 0.1 M
KCl 溶液中以 0.1 V/s 掃描速率記錄的
GSC 的 CV (a)；GSCs 的紫外-可見吸
收光譜（插圖：來自 Tauc 圖的帶隙評估）
（b）；GSC 在 5 mM K 3 Fe(CN) 6 +
0.1 M KCl 溶液中的EIS Nyquist 圖，頻
率為 0.01–10 6 Hz，振幅為 5 mV（插圖：
高頻 Nyquist 圖）(c)；GSC 在 0.1 M
Na 2 SO 4電解質中的曲線(d)。
Fig S4、 CVs of the GSCs recorded in 0.104 mM RhB + 0.01 M Na2SO4 at 0.1 V/s scan rate
在0.104 mM RhB + 0.01 M Na2SO4中以0.1 V/s掃描速率記錄的GSCs他們的CVs
回上一頁繼續講圖4b
Fig S5、FTIR spectrum of the GSCs
GSCs的FTIR光譜
Fig S6、pH of effluents for different treatment processes
不同處理過程中的出水的pH值
Fig S7、ESR spectrum for different treatment
processes
不同處理過程的ESR光譜
Fig S8、Removal efficiency of RhB in the 3D-PER using (a)
GSC and (b) GSC-15 in the presence of tert-butanol; pseudofirst-order kinetics for RhB decomposition in 3D-PER fill with
(c) GSC, and (d) GSC-15 in the presence of tert-butanol
在三維PER中使用(a)GSC和(b)GSC-15在叔丁醇存在下對RhB
的去除效率；在三維PER中填充(c)GSC和(d)GSC-15在叔丁醇
存在下對RhB分解的偽一階動力學分析
Fig. 5. TOC removal efficiency in 3D-PER fill with (a) GSC and (b) GSC-15 during continuous
operation of 11 cycles; The degradation mechanisms of RhB in the 3D-PER (c).
圖 5。(a) GSC 和 (b) GSC-15 在 11 個循環的連續運行期間 3D-PER 填充中的TOC去除效率；
RhB 在 3D-PER (c) 中的降解機制
Fig. 6. The toxicity of effluent treated by different processes with GSC (a), GSC-15 (b)
catalysts.
圖 6。使用 GSC (a)、GSC-15 (b) 催化劑通過不同程序處理的廢水的毒性。
Conclusion
• 使用 GSC 作為催化劑的 3D-PER 可實現高效的 RhB 降解。與EC和PC程
序相比，PEC程序顯示出優異的脫色和礦化性能。中空結構的 GSC-15 在
3D-PER 連續運行 11 個循環期間保持高且穩定的 RhB 去除效率。GSC15比GSC具有更強的吸附能力、優異的電化學活性和更高的光電流。在
PEC過程中，PC主要是初始化脫色，而EC在礦化中起關鍵作用。由於有
毒中間體的有效分解，RhB 的毒性在 3D-PER 中降低了 90%。3D-PER
在難降解廢水處理方面很有前景。
Conclusion
• 3D-PER using GSCs as catalysts achieves high efficiency in RhB
degradation. PEC process shows superior decolorization and
mineralization performances compared to EC and PC processes. GSC15 of hollow structure maintains high and stable removal efficiency of
RhB during continuous operation of 3D-PER for 11 cycles. GSC-15 has
stronger adsorption capability, superior electrochemical activity, and
higher photocurrent than GSC. During PEC process, PC primarily
initializes decolorization, while EC plays a critical role in mineralization.
The toxicity of RhB is reduced by 90% in 3D-PER due to the efficient
decomposition of toxic intermediates. 3D-PER is promising in refractory
wastewater treatment.
Thanks for your attention