Abstract
Here, we design and synthesize a novel 2D Cu-tetrakis(4-carboxyphenyl)porphyrin (TCPP) metal–organic framework (MOF) sheet and ultrasmall Cu5.4O nanoparticle (Cu5.4O USNP) hybrid (Cu-TCPP MOF/Cu5.4O nanocomposite). The graphene-like ultrathin Cu-TCPP MOF sheets offer high surface-to-volume atom ratios and many active sites, which is beneficial for loading more Cu5.4O USNPs. The Cu5.4O USNPs with ultrasmall size (<5 nm) have promising conductivity and excellent enzymatic ability for H2O2. The successfully prepared nanocomposites are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and Fourier transform infrared (FT-IR) techniques. The 2D graphene-like ultrathin Cu-TCPP MOF sheets show no H2O2-sensing signals, whereas Cu5.4O USNPs exhibit a clear reduction peak for detection of H2O2. Interestingly, the combination of two kinds of nanomaterials improved the H2O2 sensing ability due to their synergistic effect. The properties of the unmodified electrodes and the Cu-TCPP MOF/Cu5.4O nanocomposite-modified electrodes were systemically studied by cyclic voltammetry (CV), current-time (i-t) response, and square-wave voltammetry (SWV) techniques. The electrochemical sensor for the detection of H2O2 based on the Cu-TCPP MOF/Cu5.4O nanocomposite has a lower detection limit of 0.13 μmol·L−1 and wider linear range of 0.1 × 10−6 ~ 0.59 × 10−3 mol·L−1 and 1.59 × 10−3 ~ 20.59 × 10−3 mol·L−1 when compared with the Cu5.4O USNPs-modified electrode. The electrochemical sensor can be further used to detect H2O2 produced by cells.
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Urtizberea A, Natividad E, Alonso PJ, Andrés MA, Gascón I, Goldmann M, et al. A porphyrin spin qubit and its 2D framework nanosheets. Adv Funct Mater. 2018;28:1801695.
Dhakshinamoorthy A, Asiri AM, Garcia H. Metal-organic frameworks catalyzed C-C and C-heteroatom coupling reactions. Chem Soc Rev. 2015;44:1922–47.
Zhai Q-G, Bu X-H, Zhao X, Li D-S, Feng PY. Pore space partition in metal-organic frameworks. Acc Chem Res. 2017;50:407–17.
He T, Ni B, Zhang SM, Gong Y, Wang HQ, Gu L, et al. Ultrathin 2D zirconium metal-organic framework Nanosheets: preparation and application in Photocatalysis. Small. 2018;14:1703929.
Zhang ZJ, Nguyen HT, Miller SA, Ploskonka AM, DeCoste JB, Cohen SM. Polymer-metal-organic frameworks (polyMOFs) as water tolerant materials for selective carbon dioxide separations. J Am Chem Soc. 2016;138:920–5.
Tan C, Cao X, Wu X-J, He Q, Yang J, Zhang X, et al. Recent advances in ultrathin two-dimensional nanomaterials. Chem Rev. 2017;117:6225–331.
Huang X, Qi XY, Boey F, Zhang H. Graphene-based composites. Chem Soc Rev. 2012;41:666–86.
Alezi D, Belmabkhout Y, Suyetin M, Bhatt PM, Weselinski LJ, Solovyeva V, et al. MOF crystal chemistry paving the way to gas storage needs: aluminum-based soc-MOF for CH4, O2, and CO2 storage. J Am Chem Soc. 2015;137:13308–18.
Li H, Wang KC, Sun YJ, Lollar CT, Li JL, Zhou H-C. Recent advances in gas storage and separation using metal-organic frameworks. Mater Today. 2018;21:108–21.
Assen AH, Yassine O, Shekhah O, Eddaoudi M, Salama KN. MOFs for the sensitive detection of Ammonia: deployment of fcu-MOF thin films as effective chemical capacitive sensors. ACS Sens. 2017;2:1294–301.
Wu SY, Min H, Shi W, Cheng P. Multicenter Metal-Organic Framework-Based Ratiometric Fluorescent Sensors. Adv Mater. 2019;32:1805871.
Zhou GX, Wang YS, Jin ZK, Zhao PH, Zhang H, Wen YY, et al. Porphyrin-palladium hydride MOF nanoparticles for tumor-targeting photoacoustic imaging-guided Hydrogenothermal Cancer therapy. Nanoscale Horiz. 2019;4:1185.
Zhang W, Lu J, Gao XN, Li P, Zhang W, Ma Y, et al. Enhanced photodynamic therapy by reduced levels of intracellular glutathione obtained by employing a Nano-MOF with CuII as the active center. Angew Chem Int Ed. 2018;57:4985–90.
Liang ZB, Qu C, Xia DG, Zou RQ, Xu Q. Atomically dispersed metal sites in MOF-BasedMaterials for Electrocatalytic and photocatalytic energy conversion. Angew Chem Int Ed. 2018;57:9604–33.
Dhakshinamoorthy A, Asiri AM, Garcia H. Metal-organic framework (MOF) compounds: Photocatalysts for redox reactions and solar fuel production. Angew Chem Int Ed. 2016;55:5414–45.
Park J, Xu M, Li FY, Zhou H-C. 3D long-range triplet migration in a water-stable metal-organic framework for Upconversion-based ultralow-power in vivo imaging. J Am Chem Soc. 2018;140:5493–9.
Muldoon PF, Collet G, Eliseeva SV, Luo T-Y, Petoud S, Rosi NL. Ship-in-a-bottle preparation of long wavelength molecular antennae in lanthanide metal-organic frameworks for biological imaging. J Am Chem Soc. 2020;142:8776–81.
Kim S, Wang H, Lee YM. 2D nanosheets and their composite membranes for water, gas, and ion separation. Angew Chem Int Ed. 2019;131:17674–89.
Pen Y, Li YS, Ban YJ, Jin H, Jiao WM, Liu XL, et al. Metal-organic framework Nanosheets as building blocks for molecular sieving membranes. Science. 2014;346:1356–9.
Song F, Hu XL. Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis. Nat Commun. 2014;5:1–9.
Zhao YW, Wang JN, Pei RJ. Micron-sized ultrathin metal-organic framework sheet. J Am Chem Soc. 2020;142:10331–6.
Rodriguez-San-Miguel D, Amo-Ochoa P, Zamora F. MasterChem: cooking 2D-polymers. Chem Commun. 2016;52:4113–27.
Beldon PJ, Tominaka S, Singh P, Dasgupta TS, Bithell EG, Cheetham AK. Layered structures and nanosheets of pyrimidinethiolate coordination polymers. Chem Commun. 2014;50:3955–7.
Zheng ZK, Grünker R, Feng XL. Synthetic two-dimensional materials: a new paradigm of membranes for ultimate separation. Adv Mater. 2016;28:6529–45.
Bai WS, Li SJ, Ma JP, Cao W, Zheng JB. Ultrathin 2D metal–organic framework (nanosheets and nanofilms)-based xD-2D hybrid nanostructures as biomimetic enzymes and supercapacitors. J Mater Chem A. 2019;7:9086–98.
Hu LZ, Yuan YL, Zhang L, Zhao JM, Majeed S, Xu GB. Copper nanoclusters as peroxidase mimetics and their applications to H2O2 and glucose detection. Anal Chim Acta. 2013;762:83–6.
Ferreira CA, Ni D, Rosenkrans ZT, Cai W. Scavenging of reactive oxygen and nitrogen species with nanomaterials. Nano Res. 2018;11:4955–84.
Sheng J, Chen J, Kang J, Yu Y, Yan N, Fu X-Z, et al. Octahedral Cu2O@co(OH)2 nanocages with hierarchical flake-like walls and yolk-shell structures for enhanced electrocatalytic activity. ChemCatChem. 2019;11:2520–5.
Kamaly N, He JC, Ausiello DA, Farokhzad OC. Nanomedicines for renal disease: current status and future applications. Nat Rev Nephrol. 2016;12:738–53.
Dou BT, Yang JM, Yuan R, Xiang Y. Trimetallic hybrid Nanoflower-decorated MoS2 Nanosheet sensor for direct in situ monitoring of H2O2 secreted from live Cancer cells. Anal Chem. 2018;90:5945–50.
Troll W, Wiesner R. The role of oxygen radicals as a possible mechanism of tumor promotion. Annu Rev Pharmacol Toxicol. 1985;25:509–28.
Driessens N, Versteyhe S, Ghaddhab C, Burniat A, De Deken X, Van Sande J, et al. Hydrogen peroxide induces DNA single- and double-strand breaks in thyroid cells and is therefore a potential mutagen for this organ. Endocr Relat Cancer. 2009;16:845–56.
Guo HT, Callaway JB, Ting JP. Inflammasomes: mechanism of action, role in disease, and therapeutics. Nat Med. 2015;21:677–87.
Mittal M, Siddiqui MR, Tran K, Reddy SP, Malik AB. Reactive oxygen species in inflammation and tissue injury. Antioxid Redox Signal. 2014;20:1126–67.
Ferrucci L, Fabbri E. Inflammageing: chronic inflammation in ageing, cardiovascular disease, and frailty. Nat Rev Cardiol. 2018;15:505–22.
Xu G, Yamada T, Otsubo K, Sakaida S, Kitagawa H. Facile “modular assembly” for fast construction of a highly oriented crystalline MOF Nanofilm. J Am Chem Soc. 2012;134:6524–16527.
Ma JP, Bai WS, Zheng JB. Non-enzymatic electrochemical hydrogen peroxide sensing using a nanocomposite prepared from silver nanoparticles and copper (II)-porphyrin derived metal-organic framework nanosheets. Microchim Acta. 2019;186:482.
Liu TF, Xiao BW, Xiang F, Tan JL, Chen Z, Zhang XR, et al. Ultrasmall copper-based nanoparticles for reactive oxygen species scavenging and alleviation of inflammation related diseases. Nat Commun. 2020;11:1–16.
Thakur B, Bernalte E, Smith JP, Linton PE, Sawant SN, Banks CE, Foster CW, The Mediatorless electroanalytical sensing of sulfide utilizing unmodified graphitic electrode materials. C. 2016;2:14.
Peng C, Zhou SY, Zhang XM, Zeng TQ, Zhang W, Li HM, et al. One pot synthesis of nitrogen-doped hollow carbon spheres with improved electrocatalytic properties for sensitive H2O2 sensing in human serum. Sensor Actuat B-Chem. 2018;270:530–7.
Ramezani H, Azizi SN, Hosseini SR. NaY zeolite as a platform for preparation of ag nanoparticles arrays in order to construction of H2O2 sensor. Sensors Actuators B. 2017;248:571–9.
Gholami M, Koivisto B. A flexible and highly selective non-enzymatic H2O2 sensor based onsilver nanoparticles embedded into Nafion. Appl Surf Sci. 2019;467:112–8.
Jamal M, Hasan M, Mathewson A, Razeeb KM. Non-enzymatic and highly sensitive H2O2 sensor based on Pd nanoparticle modified gold nanowire Array electrode. J Electrochem Soc. 2012;159:B825.
Tao Y, Chang Q, Liu QH, Yang GL, Guan HT, Chen G, et al. Highly sensitive nonenzymatic H2O2 sensor based on NiFe-layered double hydroxides nanosheets grown on Ni foam. Surf Interfaces. 2018;12:102–7.
Lopa NS, Rahman MM, Ahmed F, Sutradhar SC, Ryu T, Kim W. A base-stable metal-organicframework for sensitive and non-enzymatic electrochemical detection of hydrogen peroxide. Electrochim Acta. 2018;274:49–56.
Cai JJ, Ding SL, Chen G, Sun YL, Xie Q. In situ electrodeposition of mesoporous aligned α-Fe2O3 nanoflakes for highly sensitive nonenzymatic H2O2 sensor. Appl Surf Sci. 2018;456:302–6.
Acknowledgements
The authors gratefully acknowledge the financial support for this project by the National Key R&D Program of China (2019YFC1606703), the Natural Science Foundation of Shaanxi Province in China (2020JM-429), and the National Science Foundation of China (31801653).
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Qiao, X., Arsalan, M., Ma, X. et al. A hybrid of ultrathin metal-organic framework sheet and ultrasmall copper nanoparticles for detection of hydrogen peroxide with enhanced activity. Anal Bioanal Chem 413, 839–851 (2021). https://doi.org/10.1007/s00216-020-03038-0
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DOI: https://doi.org/10.1007/s00216-020-03038-0