Enhanced Photocatalytic Degradation of Rhodamine B by Pd and PdCu Nanoparticles-Decorated ZnO

doi:10.12422/j.issn.1006-396X.2026.04.005

Abstract

Abstract:

This study is dedicated to enhancing the photocatalytic performance of rod-like ZnO via surface modification with Pd and PdCu nanoparticles, with the goal of extending its spectral response and suppressing the recombination of photogenerated charge carriers. Rod-shaped ZnO was synthesized via the solvothermal method, with the total metal mass fraction controlled at 3%. The structural and optical properties of Pd/ZnO and PdCu/ZnO were comparatively investigated and correlated with their catalytic performance. Experimental results demonstrated that both Pd and PdCu modifications triggered a localized surface plasmon resonance effect, which facilitated the separation of photogenerated electron–hole pairs and enhanced visible-light harvesting efficiency. Compared with PdCu/ZnO, although Pd/ZnO exhibits a wider band gap and a lower proportion of oxygen vacancies, it demonstrates a stronger separation capability for photogenerated carriers and thus achieves higher degradation efficiency. After 30 minutes of light irradiation, the RhB degradation rate of Pd/ZnO reaches 99.7%.Moreover,Pd/ZnO possesses excellent stability, with the degradation rate remaining at 96.9% after five cycling tests.

Key words: Photocatalysis, Zinc oxide, Solvothermal method, Bimetallic loading, Dye degradation

摘要：

采用Pd和PdCu纳米粒子对棒状ZnO进行修饰，以拓宽ZnO光谱响应范围及降低光生载流子复合率，进而提高其光催化活性。通过溶剂热法合成棒状ZnO，控制金属总质量分数为3%，对比探究了Pd/ZnO和PdCu/ZnO的结构及光学特性，并关联了其催化性能。结果表明，Pd和PdCu修饰均会产生局域表面等离子体共振效应，促进光生电子与空穴的分离，提高可见光利用率；与Pd/ZnO相比，PdCu/ZnO虽具有更小的禁带宽度及更高的氧空位占比，但Pd/ZnO对光生载流子的分离能力更强，因而具有更高的降解效率；Pd/ZnO光照30 min后，RhB降解率达到99.7%，且具有优异的稳定性，经5次循环测试后降解率仍保持在96.9%。

关键词: 光催化, 氧化锌, 溶剂热法, 双金属负载, 染料降解

CLC Number:

TQ426.8

Jiping HE, Ying ZHANG. Enhanced Photocatalytic Degradation of Rhodamine B by Pd and PdCu Nanoparticles-Decorated ZnO[J]. Journal of Petrochemical Universities, 2026, 39(4): 46-53.

贺季平, 张影. Pd和PdCu纳米粒子修饰ZnO光催化降解RhB性能[J]. 石油化工高等学校学报, 2026, 39(4): 46-53.

0
/ / Recommend

Add to citation manager EndNote|Ris|BibTeX

URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2026.04.005

https://journal.lnpu.edu.cn/syhg/EN/Y2026/V39/I4/46

Figures/Tables 7

Fig.1 XRD pattern of ZnO,Pd/ZnO and PdCu/ZnO

Fig.2 TEM and HRTEM images of ZnO, Pd/ZnO and PdCu/ZnO

Fig.3 XPS spectra and oxygen content of the photocatalysts

Fig.4 UV-vis DRS spectrum and Tauc-Plot of ZnO， Pd/ZnO and PdCu/ZnO

Fig.5 Photoluminescence spectra of ZnO，Pd/ZnO and PdCu/ZnO

Fig.6 Comparative performance of three photocatalysts and cycling stability for Pd/ZnO

Fig.7 Schematic diagram of photocatalytic degradation mechanism for Pd/ZnO

References 34

[1]	鞠雪敏，罗莉涛，张鸿涛，等. 染料行业废水无害化处理技术现状及发展趋势［J］. 科技导报， 2021， 39（17）： 45-54.
	JU X M， LUO L T， ZHANG H T， et al. Current situation and development trend of harmless treatment technology for dye wastewater in fine chemical industry［J］. Science & Technology Review， 2021， 39（17）： 45-54.
[2]	王玉尘. 石墨阳极氧化染料废水的应用［J］. 东北石油大学学报， 2018， 42（4）： 109-115.
	WANG Y C. Application of anodic oxidation treatment of dye wastewater at a graphite anode［J］. Journal of Northeast Petroleum University， 2018， 42（4）： 109-115.
[3]	郭振莲，牟庆平，李新，等. CdS/CeO₂异质结纳米光催化剂催化还原CO₂的研究［J］. 石油炼制与化工， 2023， 54（6）： 46-54.
	GUO Z L， MU Q P， LI X， et al. Study on CO₂ reduction by CdS/CeO₂ heterojunction nano-photocatalyst［J］. Petroleum Processing and Petrochemicals， 2023， 54（6）： 46-54.
[4]	张秀丽，王延明，李春虎. 微生物燃料电池耦合光催化技术降解葡萄酒清洗废水研究［J］. 当代化工， 2024， 53（1）： 63-67.
	ZHANG X L， WANG Y M， LI C H. Study on degradation of wine production wastewater by microbial fuel cell coupled photocatalytic technology［J］. Contemporary Chemical Industry， 2024， 53（1）： 63-67.
[5]	宋悦，吴限，马诚，等. 木质素改性ZnO/CeO₂异质结的紫外屏蔽性能研究［J］. 辽宁石油化工大学学报， 2024， 44（3）： 10-16.
	SONG Y， WU X， MA C， et al. Study on UV shielding properties of lignin modified ZnO/CeO₂ heterojunctions［J］. Journal of Liaoning Petrochemical University， 2024， 44（3）： 10-16.
[6]	何习楠，张晓楠，谢勋杰，等. 多维异质结光催化剂g-C₃N₄/WO₃的制备及应用［J］. 化工环保， 2024， 44（2）： 249-256.
	HE X N， ZHANG X N， XIE X J， et al. Preparation and application of multi-dimensional heterojunction photocatalyst g-C₃N₄/WO₃［J］. Environmental Protection of Chemical Industry， 2024， 44（2）： 249-256.
[7]	杜意恩，杨召弟，李玉梅. TiO₂/Fe₂O₃纳米复合材料的制备及光催化性能［J］. 辽宁石油化工大学学报， 2023， 43（4）： 1-7.
	DU Y E， YANG Z D， LI Y M. Synthesis and photocatalytic performance of TiO₂/Fe₂O₃ composites［J］. Journal of Liaoning Petrochemical University， 2023， 43（4）： 1-7.
[8]	王嘉曼，熊靖，师金鸽，等. TiO₂催化剂催化CO₂还原的研究进展［J］. 石油化工高等学校学报， 2024， 37（4）： 1-11.
	WANG J M， XIONG J， SHI J G， et al. An overview of carbon dioxide catalyzed by titanium dioxide catalyst［J］. Journal of Petrochemical Universities， 2024， 37（4）： 1-11.
[9]	王迎霄，张春来，郝英东，等. AgCl/ZnO上CH₄光催化部分氧化制HCHO性能研究［J］. 低碳化学与化工， 2024， 49（8）： 46-56.
	WANG Y X， ZHANG C L， HAO Y D， et al. Study on performance of photocatalytic partial oxidation of CH₄ to HCHO on AgCl/ZnO［J］. Low-Carbon Chemistry and Chemical Engineering， 2024， 49（8）： 46-56.
[10]	CAO H M， LIU Z， LIU T Z， et al. Well-organized assembly of ZnO hollow cages and their derived Ag/ZnO composites with enhanced photocatalytic property［J］. Materials Characterization， 2020， 160： 110125.
[11]	LIANG S H， LI S B， SHEN M S， et al. Ag-loaded ZnO nanocomposite films as photocatalysts for the degradation of pigments under visible light［J］. ACS Applied Nano Materials， 2024， 7（4）： 4518-4527.
[12]	GÜY N， ÖZACAR M. The influence of noble metals on photocatalytic activity of ZnO for Congo red degradation［J］. International Journal of Hydrogen Energy， 2016， 41（44）： 20100-20112.
[13]	LIU R J， FU X N， GUO Y F， et al. A study on Ag or Ce doped and co-doped ZnO for the photocatalytic degradation of RhB dye［J］. Vacuum， 2023， 215： 112337.
[14]	LI J H， HUANG Y L， LUO B， et al. Efficient photothermal-assisted photocatalytic hydrogen production over a plasmonic CuNi bimetal cocatalyst［J］. Journal of Colloid and Interface Science， 2022， 626： 975-984.
[15]	WEI Y W， SHAHID M Z， LYU S， et al. One-pot， ligand-free， room-temperature synthesis of Au/Pd/ZnO nanoclusters with ultra-low noble metal loading and synergistically improved photocatalytic performances［J］. RSC Advances， 2021， 11（37）： 22618-22624.
[16]	NOUA A E， KAYA D， SIGIRCIK G， et al. Enhanced photocatalytic activity in AgCu-decorated ZnO nanoparticles under UV and sunlight［J］. Journal of Materials Science： Materials in Electronics， 2024， 35（18）： 1220.
[17]	GAO T T， SHI W， ZHANG Y， et al. Finely controlled platinum nanoparticles over ZnO nanorods for selective hydrogenation of 3-nitrostyrene to 3-vinylaniline［J］. Chemistry， 2020， 26（41）： 8990-8996.
[18]	GU Z L， XIONG Z P， REN F F， et al. Flower-like PdCu catalyst with high electrocatalytic properties for ethylene glycol oxidation［J］. Journal of the Taiwan Institute of Chemical Engineers， 2018， 83： 32-39.
[19]	CASEY É， HOLMES J D， COLLINS G. PdAu nanosheets for visible-light-driven suzuki cross-coupling reactions［J］. ACS Applied Nano Materials， 2022， 5（11）： 16196-16206.
[20]	AL-GAASHANI R， RADIMAN S， DAUD A R， et al. XPS and optical studies of different morphologies of ZnO nanostructures prepared by microwave methods［J］. Ceramics International， 2013， 39（3）： 2283-2292.
[21]	ZHOU H T， CONG L J， MA J G， et al. High gain broadband photoconductor based on amorphous Ga₂O₃ and suppression of persistent photoconductivity［J］. Journal of Materials Chemistry C， 2019， 7（42）： 13149-13155.
[22]	ZHANG R H， WANG H， TWANG S Y， et al. Photocatalytic oxidative dehydrogenation of ethane using CO₂ as a soft oxidant over Pd/TiO₂ catalysts to C₂H₄ and syngas［J］. ACS Catalysis， 2018， 8（10）： 9280-9286.
[23]	LU Y H， LIN W H， YANG C Y， et al. A facile green antisolvent approach to Cu²⁺-doped ZnO nanocrystals with visible-light-responsive photoactivities［J］. Nanoscale， 2014， 6（15）： 8796-8803.
[24]	SHINDE V R， GUJAR T P， LOKHANDE C D， et al. Mn doped and undoped ZnO films： A comparative structural， optical and electrical properties study［J］. Materials Chemistry and Physics， 2006， 96（2-3）： 326-330.
[25]	SAINI S， SAINI P， KUMAR K， et al. Unlocking the molecular behavior of natural amine-targeted carbon quantum dots for the synthesis of diverse pharmacophore scaffolds via an unusual nanoaminocatalytic route［J］. ACS Applied Materials & Interfaces， 2023， 15（42）： 49083-49094.
[26]	ZHAO R Y， SUN X X， JIN Y R， et al. Au/Pd/g-C₃N₄ nanocomposites for photocatalytic degradation of tetracycline hydrochloride［J］. Journal of Materials Science， 2019， 54（7）： 5445-5456.
[27]	WEI Y W， SHAHID M Z， LYU S， et al. One-pot， ligand-free， room-temperature synthesis of Au/Pd/ZnO nanoclusters with ultra-low noble metal loading and synergistically improved photocatalytic performances［J］. RSC Advances， 2021， 11（37）： 22618-22624.
[28]	DE MARCHI S， NÚÑEZ-SÁNCHEZ S， BODELÓN G， et al. Pd nanoparticles as a plasmonic material： Synthesis， optical properties and applications［J］. Nanoscale， 2020， 12（46）： 23424-23443.
[29]	HU W Y， LI Q Y， XU D， et al. Rapidly and mildly transferring anatase phase of graphene-activated TiO₂ to rutile with elevated Schottky barrier： Facilitating interfacial hot electron injection for Vis-NIR driven photocatalysis［J］. Nano Research， 2022， 15（12）： 10142-10147.
[30]	ZHONG J B， LI J Z， HE X Y， et al. Improved photocatalytic performance of Pd-doped ZnO［J］. Current Applied Physics， 2012， 12（3）： 998-1001.
[31]	KASHYAP T， BISWAS S， AHMED S， et al. Plasmon activation versus plasmon quenching on the overall photocatalytic performance of Ag/Au bimetal decorated g-C₃N₄ nanosheets under selective photoexcitation： A mechanistic understanding with experiment and theory［J］. Applied Catalysis B-Environmental， 2021， 298： 120614.
[32]	YUE W J， WANG Z， GONG J T， et al. Synthesis of tetrapod CdS by one-pot solvothermal method for photodegradation to rhodamine B［J］. Materials Science in Semiconductor Processing， 2021， 126： 105671.
[33]	YANG J， JU Y M， LI F F， et al. Simultaneous enhanced generation of reactive oxygen species and H₂ over Pd-（Cu-s-FeO） trimetal for bifunctional catalytic degradation of refractory combined pollutants［J］. Journal of Cleaner Production， 2024， 434： 139799.
[34]	HE W W， WU H H， WAMER W G， et al. Unraveling the enhanced photocatalytic activity and phototoxicity of ZnO/metal hybrid nanostructures from generation of reactive oxygen species and charge carriers［J］. ACS Applied Materials & Interfaces， 2014， 6（17）： 15527-15535.