Cu2O/Cu Hollow Spherical Heterojunction Photocatalysts Prepared by Wet Chemical Approach

doi:10.15541/jim20240370

Abstract

Abstract:

As visible light photocatalysts, narrow bandgap semiconductors can effectively convert solar energy to chemical energy, exhibiting potential applications in alleviating energy shortage and environmental pollution. Cu₂O/Cu hollow spherical heterojunction photocatalysts were prepared by one-pot solvothermal method without any template using CuCl₂·H₂O as precursor, H₃NO·HCl and NaBH₄ as reducing agents. Morphologies, crystal structures, composition, specific surface areas, and optical properties of the products were analyzed. Addition of NaBH₄ gradually changes the morphology of Cu₂O/Cu from hollow truncated octahedra to hollow nanospheres. Thickness of Cu layer on surface of Cu₂O can be easily controlled by tuning amount of NaBH₄. Direct reduction of Cu₂O by NaBH₄ leads to intimate contact between Cu₂O and Cu interfaces, which is favorable for carrier separation and transport. Meanwhile, surface plasmon resonance effect of Cu promotes the absorption capability of Cu₂O/Cu to visible light, thus the prepared hollow sphere Cu₂O/Cu particles exhibit a higher photodegradation capability for methyl orange (MO) and colorless enrofloxacin (ENR). Catalytic performance of Cu₂O/Cu is very stable, with no significant change in its photocatalytic efficiency for MO after five recycles. Free-radical removal experiments indicate that ∙O₂^- and holes were dominant species during the MO degradation. Higher photodegradation capability of Cu₂O/Cu for MO is attributed to synergistic effect of Cu₂O and Cu. This study provides a promising strategy for preparation of heterojunction photocatalysts.

Key words: Cu₂O/Cu heterojunction, hollow nanosphere, photocatalysis, thickness of Cu layer

CLC Number:

TQ426
O644

JIA Xianghua, ZHANG Huixia, LIU Yanfeng, ZUO Guihong. Cu₂O/Cu Hollow Spherical Heterojunction Photocatalysts Prepared by Wet Chemical Approach[J]. Journal of Inorganic Materials, 2025, 40(4): 397-404.

Figures/Tables 12

Fig. 1 XRD patterns of the pure Cu2O and Cu2O/Cu samples

Fig. 2 SEM images of the pure Cu2O and Cu2O/Cu samples (a) Pure Cu2O; (b-f) Cu2O/Cu with 50 mL addition of NaBH4 at concentration of (b) 0.0067, (c) 0.0080, (d) 0.0100, (e) 0.0130, and (f) 0.0200 mol/L

Fig. 3 TEM images of Cu2O/Cu-0.0080 sample at (a) low and (b) high magnifications

Fig. 4 XPS spectra of Cu2O/Cu-0.0080 sample (a) Survey spectrum; (b) Cu2p; (c) Cu-LMM Auger spectrum; (d) O1s

Fig. 5 UV-Vis diffuse reflection spectra of the pure Cu2O and Cu2O/Cu samples Colorful figure is available on website

Fig. 6 PL spectra of the pure Cu2O and Cu2O/Cu samples

Fig. 7 N2 adsorption-desorption isotherms of the pure Cu2O and Cu2O/Cu samples Colorful figure is available on website

Table 1 Specific surface area, average pore diameter and pore volume of the pure Cu2O and Cu2O/Cu samples

Sample	Specific surface area/(cm²·g^-1)	Average pore diameter/nm	Pore volume/ (cm³·g^-1)
Pure Cu₂O	34.23	85.23	0.286
Cu₂O/Cu-0.0067	37.11	55.34	0.279
Cu₂O/Cu-0.0080	39.01	34.24	0.274
Cu₂O/Cu-0.0100	41.19	32.56	0.263
Cu₂O/Cu-0.0130	64.45	30.26	0.246
Cu₂O/Cu-0.0200	88.79	26.35	0.221

Fig. 8 Catalytic performance of the pure Cu2O and Cu2O/Cu catalysts for MO and ENR (a) Catalytic degradation curves of the pure Cu2O and Cu2O/Cu catalysts for MO; (b) Fitting plots of pseudo-first-order kinetics; (c) Absorption spectra of Cu2O/Cu-0.0080 catalyst for ENR

Fig. 9 Cycle stability of Cu2O/Cu-0.0080 sample for photocatalysis of MO

Fig. 10 Time-dependent surface temperature changes of the pure Cu2O and Cu2O/Cu samples (a) Time-dependent surface temperature under irradiation with inset showing infrared thermal image of Cu2O/Cu-0.0130 sample irradiated for 8 min; (b) Time-dependent surface temperature during photocatalysis with inset showing infrared thermal image of Cu2O/Cu-0.0130 sample photocatalytic degradation for 30 min

Fig. 11 Free radical capture experiment of Cu2O/Cu-0.0080 sample for photocatalytic degradation of MO

References 36

[1]	SINGHA A, KAISHYOP J, KHAN T S, et al. Visible-light-driven toluene oxidation to benzaldehyde over WO₃ nanostructures. ACS Applied Nano Materials, 2023, 6(23):21818.
[2]	JIAN L, ZHAO H, DONG Y M, et al. Graphite carbon ring modified carbon nitride with a strong built-in electric field for high photocatalysis-self-Fenton performance. Catalysis Science & Technology, 2022, 12(24):7379.
[3]	TOE C Y, LAMERS M, DITTRICH T, et al. Facet-dependent carrier dynamics of cuprous oxide regulating the photocatalytic hydrogen generation. Materials Advances, 2022, 3(4): 2200.
[4]	ONG W J, TAN L L, CHAI S P, et al. Highly reactive {001} facets of TiO₂-based composites: synthesis, formation mechanism and characterization. Nanoscale, 2014, 6(4): 1946.
[5]	YANG C, LIU Z L, SU Z L, et al. Combined effect of oxygen vacancies and mesopore sizes in ZnO/SiO₂ adsorbents on boosting the H₂S removal efficiency in moist conditions. Advanced Functional Materials, 2024, 34(49):2409214.
[6]	LI W J, DA P M, ZHANG Y Y, et al. WO₃ nanoflakes for enhanced photoelectrochemical conversion. ACS Nano, 2014, 8(11):11770.
[7]	BANIAMERIAN H, SHOKROLLAHZADEH S, SAFAVI M, et al. Visible-light-activated Fe₂O₃-TiO₂ nanoparticles enhance biofouling resistance of polyethersulfone ultrafiltration membranes against marine algae Chlorella vulgaris. Scientific Reports, 2024, 14: 24831.
[8]	XIONG L K, ZHANG X, CHEN L, et al. Geometric modulation of local CO flux in Ag@Cu₂O nanoreactors for steering the CO₂RR pathway toward high-efficacy methane production. Advanced Materials, 2021, 33(32):2101741.
[9]	LIU W Q, BAI P Y, WEI S L, et al. Electron-rich Cu⁰-Cu₂O heterogeneous interface constructed via controllable electrochemical reconstruction for a single CO₂ deep-reduction product ethylene. Applied Catalysis B: Environment and Energy, 2024, 348: 123831.
[10]	KIM H E, WI D H, LEE J S, et al. Photoelectrochemical nitrate and nitrite reduction using Cu₂O photocathodes. ACS Energy Letters, 2024, 9(5): 1993.
[11]	WU E T, HUANG M H. Photocatalytic oxidative amine coupling with 4-nitrophenylacetylene-modified Cu₂O polyhedra. ACS Catalysis, 2023, 13(22):14746.
[12]	CHEN B H, KUMAR G, WEI Y J, et al. Experimental revelation of surface and bulk lattices in faceted Cu₂O crystals. Small, 2023, 19(44):2303491.
[13]	ZHANG Y Y, CHEN Y X, WANG X W, et al. Low-coordinated copper facilitates the CH₂CO affinity at enhanced rectifying interface of Cu/Cu₂O for efficient CO₂-to-multicarbon alcohols conversion. Nature Communications, 2024, 15:* 5172.
[14]	ZHANG Z H, SONG R, YU Z Y, et al. Crystal-plane effect of Cu₂O templates on compositions, structures and catalytic performance of Ag/Cu₂O nanocomposites. CrystEngComm, 2019, 21(12): 2002.
[15]	ZHU M Y, CHENG Y K, LUO Q, et al. A review of synthetic approaches to hollow nanostructures. Materials Chemistry Frontiers, 2021, 5(6):2552.
[16]	ZHANG F, LIU T Y, LI M Y, et al. Multiscale pore network boosts capacitance of carbon electrodes for ultrafast charging. Nano Letters, 2017, 17(5):3097. DOI PMID
[17]	POOLAKKANDY R R, MENAMPARAMBATH M M. Soft- template-assisted synthesis: a promising approach for the fabrication of transition metal oxides. Nanoscale Advances, 2020, 2(11):5015.
[18]	CUI L L, WANG C C, ZHANG H W, et al. Facile one-step dialysis strategy for fabrication of hollow complex nanoparticles. Chemical Communications, 2019, 55(62):9120. DOI PMID
[19]	FANG Y J, YU X Y, LOU X W. Formation of hierarchical Cu-doped CoSe₂ microboxes via sequential ion exchange for high-performance sodium-ion batteries. Advanced Materials, 2018, 30(21):1706668.
[20]	DONG Y L, TAO F F, WANG L X, et al. One-pot preparation of hierarchical Cu₂O hollow spheres for improved visible-light photocatalytic properties. RSC Advances, 2020, 10(38):22387.
[21]	LV T T, XING H Z, YANG H M, et al. Rapid synthesis of Cu₂O hollow spheres at low temperature and their catalytic performance for the decomposition of ammonium perchlorate. CrystEngComm, 2021, 23(45):7985.
[22]	LIU B Q, YAO X, ZHANG Z J, et al. Synthesis of Cu₂O nanostructures with tunable crystal facets for electrochemical CO₂ reduction to alcohols. ACS Applied Materials & Interfaces, 2021, 13(33):39165.
[23]	ZHOU B, LIU Z G, ZHANG H J, et al. One-pot synthesis of Cu₂O/Cu self-assembled hollow nanospheres with enhanced photocatalytic performance. Journal of Nanomaterials, 2014, 2014: 291964.
[24]	CHANG J Y, BAO Q W, ZHANG C, et al. Rapid preparation and photocatalytic properties of octahedral Cu₂O@Cu powders. Advanced Powder Technology, 2021, 32(1):144.
[25]	CHANG Y, TEO J J, ZENG H C. Formation of colloidal CuO nanocrystallites and their spherical aggregation and reductive transformation to hollow Cu₂O nanospheres. Langmuir, 2005, 21(3):1074. PMID
[26]	ZHU S C, CHEN Z Y, LIU Z P, et al. Thermodynamics and catalytic activity of the reduced Cu on a Cu₂O surface from machine learning atomic simulation. ACS Materials Letters, 2024, 6(8):3690.
[27]	YUE Y M, ZHANG P X, WANG W, et al. Enhanced dark adsorption and visible-light-driven photocatalytic properties of narrower-band-gap Cu₂S decorated Cu₂O nanocomposites for efficient removal of organic pollutants. Journal of Hazardous Materials, 2020, 384: 121302.
[28]	BAO Y C, CHEN K Z. A novel Z-scheme visible light driven Cu₂O/Cu/g-C₃N₄ photocatalyst using metallic copper as a charge transfer mediator. Molecular Catalysis, 2017, 432: 187.
[29]	SARAEV A A, KURENKOVA A Y, MISHCHENKO D D, et al. Cu/TiO₂ photocatalysts for CO₂ reduction: structure and evolution of the cocatalyst active form. Transactions of Tianjin University, 2024, 30(2):140.
[30]	XU B G, WANG B, ZHANG H Y, et al. Z-scheme Cu₂O nanoparticle/graphite carbon nitride nanosheet heterojunctions for photocatalytic hydrogen evolution. ACS Applied Nano Materials, 2022, 5(6):8475.
[31]	LI Z J, WANG M Z, JIA Y Y, et al. CeO₂/Cu₂O/Cu tandem interfaces for efficient water-gas shift reaction catalysis. ACS Applied Materials & Interfaces, 2023, 15(26):31584.
[32]	LI D Y, ZAN J, WU L P, et al. Heterojunction tuning and catalytic efficiency of g-C₃N₄-Cu₂O with glutamate. Industrial & Engineering Chemistry Research, 2019, 58(10):4000.
[33]	ZHANG Z J, WANG W Z, GAO E P, et al. Photocatalysis coupled with thermal effect induced by SPR on Ag-loaded Bi₂WO₆ with enhanced photocatalytic activity. The Journal of Physical Chemistry C, 2012, 116(49):25898.
[34]	WANG Y B, ZHAO X, CAO D, et al. Peroxymonosulfate enhanced visible light photocatalytic degradation bisphenol A by single-atom dispersed Ag mesoporous g-C₃N₄ hybrid. Applied Catalysis B: Environmental, 2017, 211: 79.
[35]	MEI W D, LI D Y, XU H M, et al. Effect of electronic migration of MIL-53(Fe) on the activation of peroxymonosulfate under visible light. Chemical Physics Letters, 2018, 706: 694.
[36]	ZHANG H, DIAO J F, LIU Y H, et al. In situ-grown Cu dendrites plasmonically enhance electrocatalytic hydrogen evolution on facet-engineered Cu₂O. Advanced Materials, 2023, 35(42):2305742.

Cu₂O/Cu Hollow Spherical Heterojunction Photocatalysts Prepared by Wet Chemical Approach

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 12

References 36

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	MA Binbin, ZHONG Wanling, HAN Jian, CHEN Liangyu, SUN Jingjing, LEI Caixia. ZIF-8/TiO₂ Composite Mesocrystals: Preparation and Photocatalytic Activity [J]. Journal of Inorganic Materials, 2024, 39(8): 937-944.
[2]	CAO Qingqing, CHEN Xiangyu, WU Jianhao, WANG Xiaozhuo, WANG Yixuan, WANG Yuhan, LI Chunyan, RU Fei, LI Lan, CHEN Zhi. Visible-light Photodegradation of Tetracycline Hydrochloride on Self-sensitive Carbon-nitride Microspheres Enhanced by SiO₂ [J]. Journal of Inorganic Materials, 2024, 39(7): 787-792.
[3]	WANG Zhaoyang, QIN Peng, JIANG Yin, FENG Xiaobo, YANG Peizhi, HUANG Fuqiang. Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation [J]. Journal of Inorganic Materials, 2024, 39(4): 383-389.
[4]	WU Lin, HU Minglei, WANG Liping, HUANG Shaomeng, ZHOU Xiangyuan. Preparation of TiHAP@g-C₃N₄ Heterojunction and Photocatalytic Degradation of Methyl Orange [J]. Journal of Inorganic Materials, 2023, 38(5): 503-510.
[5]	LING Jie, ZHOU Anning, WANG Wenzhen, JIA Xinyu, MA Mengdan. Effect of Cu/Mg Ratio on CO₂ Adsorption Performance of Cu/Mg-MOF-74 [J]. Journal of Inorganic Materials, 2023, 38(12): 1379-1386.
[6]	SUN Chen, ZHAO Kunfeng, YI Zhiguo. Research Progress in Catalytic Total Oxidation of Methane [J]. Journal of Inorganic Materials, 2023, 38(11): 1245-1256.
[7]	MA Xinquan, LI Xibao, CHEN Zhi, FENG Zhijun, HUANG Juntong. BiOBr/ZnMoO₄ Step-scheme Heterojunction: Construction and Photocatalytic Degradation Properties [J]. Journal of Inorganic Materials, 2023, 38(1): 62-70.
[8]	CHEN Hanxiang, ZHOU Min, MO Zhao, YI Jianjian, LI Huaming, XU Hui. 0D/2D CoN/g-C₃N₄ Composites: Structure and Photocatalytic Performance for Hydrogen Production [J]. Journal of Inorganic Materials, 2022, 37(9): 1001-1008.
[9]	XUE Hongyun, WANG Congyu, MAHMOOD Asad, YU Jiajun, WANG Yan, XIE Xiaofeng, SUN Jing. Two-dimensional g-C₃N₄ Compositing with Ag-TiO₂ as Deactivation Resistant Photocatalyst for Degradation of Gaseous Acetaldehyde [J]. Journal of Inorganic Materials, 2022, 37(8): 865-872.
[10]	CHI Congcong, QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie. Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property [J]. Journal of Inorganic Materials, 2022, 37(7): 750-756.
[11]	WANG Xiaojun, XU Wen, LIU Runlu, PAN Hui, ZHU Shenmin. Preparation and Properties of Ag@C₃N₄ Photocatalyst Supported by Hydrogel [J]. Journal of Inorganic Materials, 2022, 37(7): 731-740.
[12]	LIU Xuechen, ZENG Di, ZHOU Yuanyi, WANG Haipeng, ZHANG Ling, WANG Wenzhong. Selective Oxidation of Biomass over Modified Carbon Nitride Photocatalysts [J]. Journal of Inorganic Materials, 2022, 37(1): 38-44.
[13]	ZHANG Xian, ZHANG Ce, JIANG Wenjun, FENG Deqiang, YAO Wei. Synthesis, Electronic Structure and Visible Light Photocatalytic Performance of Quaternary BiMnVO₅ [J]. Journal of Inorganic Materials, 2022, 37(1): 58-64.
[14]	LIU Peng, WU Shimiao, WU Yunfeng, ZHANG Ning. Synthesis of Zn_0.4(CuGa)_0.3Ga₂S₄/CdS Photocatalyst for CO₂ Reduction [J]. Journal of Inorganic Materials, 2022, 37(1): 15-21.
[15]	WANG Luping, LU Zhanhui, WEI Xin, FANG Ming, WANG Xiangke. Application of Improved Grey Model in Photocatalytic Data Prediction [J]. Journal of Inorganic Materials, 2021, 36(8): 871-876.