Preparation of CeO2/CdxZn1-xS Photocatalyst and its High-Performance Photocatalytic Hydrogen Production
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摘要: 采用溶剂热法制备了CdxZn1-xS固溶体、CeO2/CdxZn1-xS异质结，并利用XRD、SEM、XPS等表征手段对其样品的晶型、形貌、结构、元素组成等进行了表征。可见光照射下，研究了CdxZn1-xS固溶体、CeO2/CdxZn1-xS异质结产氢性能。Cd0.3Zn0.7S异质结的产氢速率为3.86 mmol·g−1·h−1，分别是CdS、ZnS的4.85、11.03倍。当CeO2负载比例为10%时，CeO2/Cd0.3Zn0.7S异质结具有最佳的光催化性能，产氢速率为7.89 mmol·g−1·h−1，分别是CeO2、Cd0.3Zn0.7S固溶体的40.25、2.04倍。光照下，CeO2的电子迁移到CdxZn1-xS，使得靠近CeO2的异质结界面部分带正电，而靠近CdxZn1-xS的异质结界面部分带负电，形成内电场，增强了载流子分离与迁移性能。
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关键词:
- CeO2/CdxZn1-xS /
- 固溶体 /
- 异质结 /
- 内电场 /
- 光催化产氢
Abstract: : CdxZn1-xS solid solution and CeO2/CdxZn1-xS heterojunction were prepared by solvothermal method, and the crystal shape, morphology, structure and elemental composition were characterized by XRD, SEM and XPS. The hydrogen production properties of CdxZn1-xS solid solution and CeO2/CdxZn1-xS heterojunction were studied under visible light irradiation. The hydrogen production rate of Cd0.3Zn0.7S heterojunction was 3.86 mmol·g−1·h−1, which was 4.85 and 11.03 times that of CdS and ZnS, respectively. When the CeO2 loading ratio was 10%, the CeO2/Cd0.3Zn0.7S heterojunction had the best photocatalytic performance, and the hydrogen production rate was 7.89 mmol·g−1·h−1, which was 40.25 and 2.04 times of that of CeO2 and Cd0.3Zn0.7S solid solutions, respectively. Under light, the electrons of CeO2 migrate to CdxZn1-xS, making the part of the heterojunction interface near CeO2 positively charged, while the part of the heterojunction interface near CdxZn1-xS negatively charged, forming an internal electric field, which enhanced the carrier separation and migration performance. -
图 4 (a) CZS-0.3的SEM图，(b) CeO2的SEM图，(c) 10% CCZS-0.3的SEM图
Figure 4. (a) SEM image of CZS-0.3, (b) SEM image of CeO2, (c) SEM image of 10% CCZS-0.3
图 5 (a-c) 10%CCZS-0.3的的HR-TEM图，(d) 210%CCZS-0.3的EDS mapping，分别为Zn、Cd、S、Ce、O
Figure 5. ((a-c) HR-TEM image of 10%CCZS-0.3, (d) EDS mapping of 10%CCZS-0.3
图 6 (a)样品的XPS全谱，样品的XPS，(b) S 2p，(c) Zn 2p，(d) Cd 3d，(e) O1s，(f) Ce3d
Figure 6. (a) XPS full spectrum of the sample, XPS of the sample, (b) S 2p，(c) Zn 2p，(d) Cd 3d，(e) O1s，(f) Ce3d
图 7 CeO2、CZS-0.3、10% CCZS-0.3的EPR光谱
Figure 7. EPR spectrum of CeO2, CZS-0.3, 10% CCZS-0.
图 8 (a) CZS-X的UV-Vis DRS谱图，(b) CeO2、CZS-0.3、10% CCZS-0.3的UV-Vis DRS谱图，(c) CeO2的带隙
Figure 8. (a) UV-Vis DRS of CZS-X, (b) The UV-Vis DRS of CeO2, CZS-0.3 and 10% CCZS-0.3, (c) Band gap of CeO2
图 9 (a) CZS-0.3的带隙，(b) CeO2的XPS价带谱，(c) CZS-0.3的XPS价带谱
Figure 9. (a) Band gap of CZS-0.3, (b) Valence-band spectrum of CeO2, (cf) Valence-band spectrum of CZS-0.3
图 10 (a)CeO2的能带结构，(b)CeO2的态密度，(c)CZS-0.3的能带结构，(d)CZS-0.3的态密度
Figure 10. (a)Band structure of CeO2, (b)Density of states for CeO2, (c)Band structure of CZS-0.3, (d) States density of CZS-0.3
图 11 (a) CZS-X的光催化产氢性能，(b) CeO2、y%CCZS-0.3的光催化产氢性能，(c) y%CCZS-0.3的光催化产氢性能，(d) 10%CCZS-0.3的产氢稳定性试验，(e) 10%CCZS-0.3反应前后XRD谱图，(f) 10%CCZS-0.3的量子效率
Figure 11. (a) Photocatalytic hydrogen production of CZS-X, (b) Photocatalytic hydrogen production of CeO2 and y%CCZS-0.3, (c) Photocatalytic hydrogen production of y%CCZS-0.3, (d) Hydrogen production stability of 10%CCZS-0.3, (e) XRD patters of before and after five cycles of 10%CCZS-0.3, (f) Apparent quantum efficiency(AEQ) of 10%CCZS-0.3
图 12 CeO2、CZS-0.3、10% CCZS-0.3的(a)瞬态光电流谱，(b)电化学阻抗谱，(c)光致发光光谱，(d-e)CZS-0.3和CeO2的Mott-Schottky曲线，(i)CZS-0.3和CeO2的能带结构示意图
Figure 12. (a) Transient photocurrent responses, (b) EIS spectra, (c) PL spectra of CeO2, CZS-0.3 and 10% CCZS-0.3, (d-e) Mott schottky curve CZS-0.3 and CeO2, (i) Band structure of CZS-0.3 and CeO2
图 14 光催化产氢机制示意图(a)CeO2与CZS-0.3接触前，(b)CeO2与CZS-0.3形成异质结后，(c)光照下10%CCZS-0.3异质结光生电荷转移途径。Ef：费米能级；CB：导带；VB：价带
Figure 14. Schematic diagram of photocatalytic hydrogen production mechanism. (a) Before forming heterojunction, (b) After forming heterojunction, (c) Photogenerated charge transfer pathway of 10%CCZS-0.3 heterojunction under light. Ef: Fermi level; CB: Conduction band; VB: Valence band
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