Colorimetric Sensing Based on Ag₂Cu₂O₃ for Detecting Hydroquinone AITranslate

［1］Movahed V，Arshadi L，Ghanavati M，Nejad E M，Mohagheghzadeh Z，Rezaei M. Simultaneous electrochemical detection of antioxidants hydroquinone，Mono-Tert-butyl hydroquinone and catechol in food and polymer samples using ZnO@MnO2-rGO nanocomposite as sensing layer［J］.Food Chemistry，2023，403：134286.

［2］Rao Q H，Hu F X，Gan L Y，Guo C，Liu Y，Zhang C，Chen C，Yang H B，Li C M. Boron-nitrogen-Co-doping nanocarbons to create rich electroactive defects toward simultaneous sensing hydroquinone and catechol［J］. Electrochimica Acta，2022，402：139427.

［3］Huang H，Chen Y，Chen Z，Chen J，Hu Y，Zhu J J. Electrochemical sensor based on Ce-MOF/carbon nanotube composite for the simultaneous discrimination of hydroquinone and catechol［J］.Journal of Hazardous Materials，2021，416：125895.

［4］Behera A，Babu P，Parida K. Growth of macroporous TiO2 on B-doped g-C3N4 nanosheets：a Z-scheme photocatalyst for H2O2 production and phenol oxidation under visible light［J］. Inorganic Chemistry Frontiers，2021，8（6）：1489.

［5］Koyappayil A，Seok H，Choi G H，Chavan S，Yeon S，Son S，Go A，Lee J，Kim K W，Dongho Lee，Choi H B，Kim H U，Kim J K，Kim T，Lee M H. Mesoporous WO3‐dot‐decorated flexible electrodes for the determination of industrial pollutants［J］.Energy & Environmental Materials，2025，8（2）：12842.

［6］Niu Y Z，Kang K，Wang B B，Wang L Y，Li C W，Gao X，Zhao Z Z，Ji X P. Ultrasensitive electrochemical sensing of catechol and hydroquinone via single-atom nanozyme anchored on MOF-derived porous carbon［J］.Talanta，2024，268：125349.

［7］Liang M N，Yuan L L，Shao C Y，Zheng X Q，Song Q C，Gu Z R，Lu S. Sequential visual sensing of H2O2 and GSH based on fluorescent copper nanoclusters incorporated eggshell membrane［J］.IEEE Sensors Journal，2023，23（16）：18142.

［8］Yuan X W，Jin Y，Guo J C，Wang Q，Xu L，Song Y J，Xiong X L. Cu single atoms embedded in N‑doped hollow carbon spheres for simultaneous electrochemical detection of hydroquinone and catechol［J］.ACS Applied Nano Materials，2024，7：14154.

［9］Zhuang Z J，Zhang C Y，Yu Z D，Liu W Y，Zhong Y J，Zhang J Y，Xu Z H. Turn-on colorimetric detection of hydroquinone based on Au/CuO nanocomposite nanozyme［J］.Microchimica Acta，2022，189：293.

［10］Wang Y，Cao X Y，Li X Y，Chen L，Chang M Q，Chen Y，Huang B C. Perovskite-structured ultrasensitive CaMnO3 nanoenzyme enables highly efficient ultrasound-amplified and catalysis-involved synergistic tumor therapy［J］. Chemical Engineering Journal，2024，496：154236.

［11］Wang X C，Chen M Y，Zhao L S. Development of a colorimetric sensing assay for ascorbic acid and sarcosine utilizing the dual-class enzyme activity of Fe3O4@SiO2@NiCo2S4［J］.Chemical Engineering Journal，2023，468：143612.

［12］Wang Y H，Ding L，Feng J，Lin Z G，Yao H L，You X Y，Zhang X L，Sun W，Liu Y，Wang P Y. Mesoporous cerium oxide nanoenzyme for efficacious impeding tumor and metastasis via conferring resistance to anoikis［J］.Biomaterials，2025，314：122876.

［13］Anand B C A，Ravikumar A，Panneerselvam P，Radhakrishnan K. A novel Hg（II） sensor based on Fe3O4@ZnO nanocomposite as peroxidase mimics［J］. Applied Surface Science，2018，449：669.

［14］Wei Z N，Li H Q，Wu J，Dong Y L，Zhang H Y，Chen H L，Ren C L. 3DRGO-NiFe2O4/NiO nanoparticles for fast and simple detection of organophosphorus pesticides［J］. Chinese Chemical Letters，2020，31（1）：177.

［15］Chai T Q，Li J X，Chen G Y，Luo M L，Yang F Q. Construction of pyrimidine derivatives-copper enzyme mimics as colorimetric sensing elements for efficient detection of phenolic compounds and hydrogen peroxide［J］. Journal of Hazardous Materials，2024，480：136294.

［16］Zhou J H，Chen H Y，Han X Y，Xu Y，Meng Y X，Tian M M，Dong T W，Chai F. Fabrication of bimetallic CuAg micro-flower with oxidase mimicking feature for colorimetric sensing of ascorbic acid in serum assisted by smartphone［J］.Separation and Purification Technology，2025，355：129819.

［17］（王芮，成先雄，连军锋，刘鑫，唐佳华，姚荣. 钴基双金属氧化物复合碳质材料活化过硫酸盐研究进展［J］.现代化工，2025，45（5）：60.）

R Wang，X X Cheng，J F Lian，X Liu，J H Tang，R Yao. Advances on cobalt-based bimetallic oxides compounding carbonaceous materials activated peroxysulfate［J］. Modern Chemical Industry，2025，45（5）：60.

［18］Jiang X R，Huang H，Luo R Z，Qv Z H，Zhang X L. Antibacterial activity and mechanism of Ag2Cu2O3 mixed-metal oxide［J］.Inorganic Chemistry Communications，2024，170：113141.

［19］Yin C K，Khan A，Gao Q H，Li Q，Zhou X Y，Liu X Y，Xu A H，Li X X. Synergistic activation of peroxymonosulfate for efficient aqueous p-nitrophenol degradation with Cu（Ⅱ） and Ag（Ⅰ） in Ag2Cu2O3［J］. Separation and Pu-rification Technology，2022，291：120934.

［20］Svintsitskiy D A，Slavinskaya E M，Kardash T Y，Avdeev V I，Senkovskiy B V，Koscheev S V，Boronin A I. Low-temperature cata-lytic CO oxidation over mixed silver–copper oxide Ag2Cu2O3［J］.Applied Catalysis A：General，2016，510：64.

［21］Kumar A，Sagar G L，Mukesh P，Hegde A，Nagaraja H S. Novel Ag2Cu2O3 nanorods as stable anode material for lithium-ion battery［J］.Journal of Power Sources，2025，641：236863.

［22］Niu P B，Wang Y Q，Hu R，Yang T. Cu nanoparticles/CoO/Carbon nanofibers as an enhanced peroxidase mimic for total antioxidant capacity assessment in drinks［J］. ACS Applied Nano Materials，2024，7（6）：5996.

［23］Liu X L，Wu F F，Zheng X Z，Liu H R，Ren F L，Sun J P，Ding H W，Yang R，Jin L. Facile synthesis of high-loading Cu single-atom nanozyme for total antioxidant capacity sensing［J］.ACS Applied Nano Materials，2023，6（12）：10303.

［24］Zhou X B，Wang M J，Chen J Y，Su X G. Cascade reaction biosensor based on Cu/N co-doped two-dimensional carbon-based nanozyme for the detection of lactose and beta-galactosidase［J］.Talanta，2022，245：123451.

［25］Tian L，Huang Z J，Na W D，Liu Y Y，Wang S，He Y，Cheng W J，Huang T Z，Li Z，Li T X. Heterojunction MnO2-nanosheet-decorated Ag nanowires with enhanced oxidase-like activity for the sensitive dual-mode de-tection of glutathione［J］.Nanoscale，2022，14（41）：15340.

［26］Wang Y，Cheng C，Ma R F，Xu Z R，Ozaki Y. In situ SERS monitor-ing of intracellular H2O2 in single living cells based on label-free bi-functional Fe3O4@Ag nanoparticles［J］.Analyst，2022，147（9）：1815.

［27］Shi Y X，Li H R，Kong X，Yang J，Lu G，Liu Q Y. NiCo2O4 with changed catalytic process and enhanced catalytic property as mimic enzyme by introducing Mo6+［J］.Colloids and Surfaces A-Physicochemical and Engineering Aspects，2023，670：131542.

［28］（于巧玲，刘成宝，曹一达，郑磊之，陈丰，钱君超，邱永斌，孟宪荣，陈志刚. SnO2 QDs-g-C3N4/C的合成及其光催化降解四环素研究［J］.稀有金属，2024，48（8）：1144.）

Q L Yu，C B Liu，Y D Cao，L Z Zheng，F Chen，J C Qian，Y B Qiu，X R Meng，Z G Chen. Synthesis of SnO2 QDs-g-C3N4/C and its photocatalytic degradation of tetracycline［J］.Chinese Journal of Rare Metals，2024，48（8）：1144.

［29］Song Y W，Zhao M G，Li H，Wang X T，Cheng Y F，Ding L J，Fan S S，Chen S G. Facile preparation of urchin-like NiCo2O4 microspheres as oxidase mimetic for colormetric assay of hydroquinone［J］.Sensors and Actuators B：Chemical，2018，255：1927.

［30］Zhang L P，Xing Y P，Liu L H，Zhou X H，Shi H C. Fenton re-action-triggered colorimetric detection of phenols in water samples using unmodified gold nanoparticles［J］.Sensors and Actuators B：Chemical，2016，225：593.

［31］Wang X，Zhao M，Song Y，Liu Q，Zhang Y，Zhuang Y，Chen S. Synthesis of ZnFe2O4/ZnO heterostructures decorated three-dimensional graphene foam as peroxidase mimetics for colori-metric assay of hydroquinone［J］.Sensors and Actuators B：Chemical，2019，283：130.

Basic Information:

DOI：10.13373/j.cnki.cjrm.XY25040022

Chinese Library Classification Number:TF803.21

Citation Information:

Hydroquinone (HQ), as an important chemical raw material and antioxidant, has been widely used in industrial production such as rubber, dyes cosmetics, antioxidant, and medical procedures. With the development of modern industry, more and more HQ pollutions are released into nature. Due to its high toxicity and persistence in ecosystems, HQ is particularly harmful to human health and environment. There is an urgent need for developing simple and sensitive methods for real-time monitoring of HQ. At present, a lot of efforts have been made to detect HQ, and many sensitive and selective methods have been used, such as mass spectrometry, electrochemical sensing, high-performance liquid chromatography, fluorescence sensing, and so on. However, most of those methods need complicated processes or expensive measurement equipment which limits its applications. Colorimetric sensing with simple preparation, low-cost and good selectivity has been focused. High-performance of transition metal oxides including Co₃O₄, Fe₃O₄, CuO, etc had been proved in the detection of heavy ions and pesticides in environment. To our best knowledge, Ag₂Cu₂O₃ as a mimic enzyme is not reported yet for now. Herein, Ag₂Cu₂O₃ nanoparticles were fabricated by a simple method and characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), and X-ray photoelectron spectroscopy (XPS). The measurement results showed that the morphology of Ag₂Cu₂O₃ was nanorods with the length 0.63~1.54 μm of and the diameter of 0.15~0.47 μm. XPS spectrum determined valence states and surface atomic compositions of Ag₂Cu₂O₃. The peaks of O 1s, Cu 2p, and Ag 3d appeared in the spectrum of Ag₂Cu₂O₃. The high-resolution XPS analysis of Cu 2p and Ag 3d showed the binding energy peaks at 374.2 and 368.3 eV were correspond to Ag⁺ oxidation state, the binding energy peaks at 953.6 and 933.75 eV were correspond to Cu²⁺ oxidation state. The high-resolution XPS analysis of O 1s showed the binding energy peaks at 529.5, 531.2 and 532.2 eV were respectively correspond to lattice oxygen (O_L), surface-adsorbed oxygen (O_A), and adsorbed H₂O (O_H2O). The oxidase-like activity of Ag₂Cu₂O₃ was measured in presence of 3, 3′, 5, 5′-tetra-methylbenzidine (TMB). Different pH values (2~8) and temperatures (5~45 ℃) were used to estimate the influences of pH and temperature on the properties of Ag₂Cu₂O₃ The highest catalytic performance of the nanorods appeared at temperature of 25 ℃ and pH of 5. The catalytic reaction of Ag₂Cu₂O₃ on TMB was explored by adding three trapping agents EDTA (ethylene diamine tetraacetic acid), IPA (isopropanol) and PBQ (1, 4-benzoquinone) to trap h⁺ (hole), ·OH (hydroxyl radical) and O₂·^- (superoxide radical) respectively. After adding EDTA and PBQ, the solution absorbance was obviously reduced, proving that lots of h⁺ and O₂·⁻ were generated during the catalytic process. Furthermore, HQ as a kind of reductive molecule could react with blue ox-TMB to form colorless TMB. According to the above abovementioned results, a colorimetric sensing platform with Ag₂Cu₂O₃ for detection of HQ was built. The absorbance and concentration of HQ had a linear relationship between 3~30 μmol·L^-1 with the limit of detection 1.67 μmol·L⁻¹ (limit of detection=3s/k, s-standard deviation of instrument response, k-slope of calibration curve). Various ion interferents (Na⁺, K⁺, Ca²⁺, Zn²⁺, NH₄⁺, Mn²⁺, Cd²⁺ and Mg²⁺) were added into detecting system to explore selective and anti-interference properties of this detecting system. The result showed that the absorption intensity of HQ was the strongest of all, even if the concentration of interferents was 10 times. Detection of HQ in river samples was evaluated by standard addition method. Considerable recovery rate demonstrated enormous potential for this method in detecting HQ in real samples.