Skip to main content
Log in

Solvothermal synthesis of transition metal (iron/copper) and nitrogen co−doped carbon nanomaterials: comparing their peroxidase−like properties

  • Research paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

In this work, iron- and nitrogen-doped carbon nanomaterials (Fe–N-CNMs) and copper- and nitrogen-doped CNMs (Cu–N-CNMs) were synthesized through a facile one-pot solvothermal approach. Their peroxidase-like properties were studied and compared. The Michaelis-constant Km of Fe–N-CNMs with H2O2 or TMB as the primary substrate is 19 µM and 78 µM at optimal conditions, respectively, while Km of Cu–N-CNMs with H2O2 or TMB as the primary substrate is 2.4 mM and 0.44 mM at optimal conditions, respectively. The Km values of both types of materials are lower than or comparable to those of horseradish peroxidase (HRP). Moreover, under the same mass concentration, Fe–N-CNMs is superior to Cu–N-CNMs in achieving higher values of the maximum reaction rate Vmax (e.g., 5.67 × 10–8 M/s for Fe–N-CNMs compared to 4.68 × 10–8 M/s for Cu–N-CNMs with H2O2 as the primary substrate). However, it was also found that under high concentrations of substrates (3,3,5,5′-tetramethylbenzidine (TMB) and hydrogen peroxide (H2O2)), the reaction rates of Fe–N-CNMs are saturated, but the reaction rates of Cu–N-CNMs are increasing versus the concentrations of substrates and are higher than those of Fe–N-CNMs. Experimental results showed that synergistic efforts of both the catalytic mechanism and the product-microaggregation process could be involved in the Cu–N-CNM-based reaction to enhance the measured reaction rates. Potential applications were discussed on the basis of the reaction characteristics of these two peroxidase-like materials.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6

Similar content being viewed by others

References

  • Cai X, Jiao L, Yan H, Wu Y, Gu W, Du D, Lin Y, Zhu C (2021) Nanozyme-involved biomimetic cascade catalysis for biomedical applications. Mater Today 44:211–228

    Article  CAS  Google Scholar 

  • Cai S, Yang R (2019) Noble Metal-Based Nanozymes. Nanozymology:331–365

  • Chen Q, Li S, Liu Y, Zhang X, Tang Y, Chai H, Huang Y (2020) Size-controllable Fe-N/C Single-atom Nanozyme with Exceptional Oxidase-like Activity for Sensitive Detection of Alkaline Phosphatase. Sensors Actuators B Chem 305:127511

    Article  CAS  Google Scholar 

  • Cheng N, Li J, Liu D, Lin Y, Du D (2019) Single-Atom Nanozyme Based on Nanoengineered Fe–N–C Catalyst with Superior Peroxidase-Like Activity for Ultrasensitive Bioassays. Small 15:1901485

    Article  CAS  Google Scholar 

  • Claramunt S, Varea A, López-Díaz D, Velázquez M, Cornet A, Cirera A (2015) The Importance of Interbands on the Interpretation of the Raman Spectrum of Graphene Oxide. J Phys Chem C 18:10123–10129

    Article  Google Scholar 

  • Dang T, Heo N, Cho H, Lee S, Song M, Kim H, Kim M (2021) Colorimetric Determination of Phenolic Compounds Using Peroxidase Mimics Based on Biomolecule-free Hybrid Nanoflowers Consisting of Graphitic Carbon Nitride and Copper. Microchim Acta 188:293

    Article  CAS  Google Scholar 

  • Du J, Qi S, Fan T, Yang Y, Wang C, Shu Q, Zhuo S, Zhu C (2021) Nitrogen and Copper-doped Carbon Quantum Dots with Intrinsic Peroxidase-like Activity for Double-signal Detection of Phenol. Analyst 146:4280–4289

    Article  CAS  Google Scholar 

  • Fan L, Sun P, Huang Y, Xu Z, Lu X, Xi J, Han K, Guo R (2020) One-Pot Synthesis of Fe/N-Doped Hollow Carbon Nanospheres with Multienzyme Mimic Activities against Inflammation. ACS Appl Bio Mater 3:1147–1157

    Article  CAS  Google Scholar 

  • Gao L, Zhuang J, Nie L, Zhang J, Zhang Y, Gu N, Wang T, Feng J, Yang D, Perrett S, Yan X (2007) Intrinsic Peroxidase-like Activity of Ferromagnetic Nanoparticles. Nat Nanotechnol 2:577–583

    Article  CAS  Google Scholar 

  • Han S, Hwang T, Yoon Y, Kang J (2011) Evidence of Singlet Oxygen and Hydroxyl Radical Formation in Aqueous Goethite Suspension Using Spin-trapping Electron Paramagnetic Resonance (EPR). Chemosphere 84:1095–1101

    Article  CAS  Google Scholar 

  • Hou Y, Lu Y, Chen Q, Zhang X, Huang Y (2021) Ultrathin Two-dimensional Carbon Nanosheets with Highly Active Cu-Nx Sites as Specific Peroxidase Mimic for Determining Total Antioxidant Capacity. Sensors Actuators B Chem 333:129549

    Article  CAS  Google Scholar 

  • Jiang D, Ni D, Rosenkrans Z, Huang P, Yan X, Cai W (2019) Nanozyme: new horizons for responsive biomedical applications. Chem Soc Rev 48:3683–3704

    Article  CAS  Google Scholar 

  • Krishnamoorthy K, Veerapandian M, Yun K, Kim S (2013) The Chemical and Structural Analysis of Graphene Oxide with Different Degrees of Oxidation. Carbon 53:38–49

    Article  CAS  Google Scholar 

  • Li S, Zhang Y, Wang Q, Lin A, Wei H (2022) Nanozyme-enabled analytical chemistry. Anal Chem 94:312–323

    Article  CAS  Google Scholar 

  • Lin L, Xiao Y, Wang Y, Zeng Y, Lin Z, Chen X (2019) Hydrothermal Synthesis of Nitrogen and Copper Co-doped Carbon Dots with Intrinsic Peroxidase-like Activity for Colorimetric Discrimination of Phenylenediamine Isomers. Microchim Acta 186:288

    Article  Google Scholar 

  • Mahmoudpour M, Ding S, Lyu Z, Ebrahimi G, Du D, Dolatabadi J, Torbati M, Lin Y (2021) Aptamer functionalized nanomaterials for biomedical applications: recent advances and new horizons. Nano Today 39:101177

    Article  CAS  Google Scholar 

  • Niu X, Shi Q, Zhu W, Liu D, Tian H, Fu S, Cheng N, Li S, Smith J, Du D, Lin Y (2019) Unprecedented Peroxidase-mimicking Activity of Single-atom Nanozyme with Atomically Dispersed Fe–Nx Moieties Hosted by MOF Derived Porous Carbon. Biosens Bioelectron 142:111495

    Article  CAS  Google Scholar 

  • Peng Y, Yu X, Yin W, Dong W, Peng J, Wang T (2020) Colorimetric Assay Using Mesoporous Fe-Doped Graphitic Carbon Nitride as a Peroxidase Mimetic for the Determination of Hydrogen Peroxide and Glucose. ACS Appl Bio Mater 3:59–67

    Article  CAS  Google Scholar 

  • Ragg R, Tahir M, Tremel W (2016) Solids go bio: inorganic nanoparticles as enzyme mimics. Eur J Inorg Chem:1906–1915

  • Sun H, Zhou Y, Ren J, Qu X (2018) Carbon nanozymes: enzymatic properties, catalytic mechanism, and applications. Angew Chem Int Ed 57:9224–9237

    Article  CAS  Google Scholar 

  • Vázquez-González M, Liao W, Cazelles R, Wang S, Yu X, Gutkin V, Willner I (2017) Mimicking Horseradish Peroxidase Functions Using Cu2+-Modified Carbon Nitride Nanoparticles or Cu2+-Modified Carbon Dots as Heterogeneous Catalysts. ACS Nano 11:3247–3253

    Article  Google Scholar 

  • Wang Q, Wei H, Zhang Z, Wang E, Dong S (2018) Nanozyme: an emerging alternative to natural enzyme for biosensing and immunoassay. TrAC Trends Anal Chem 105:218–224

    Article  CAS  Google Scholar 

  • Wang W, Wang X, Cheng N, Luo Y, Lin Y, Xu W, Du D (2020) Recent advances in nanomaterials-based electrochemical (bio)ensors for pesticides detection. TrAC Trends Anal Chem 132:116041

    Article  CAS  Google Scholar 

  • Wang L, Xue J, Chang J, Yu C, Dai H, Yao Z, Zhou J, Sun G, Huang W (2021) Fe, N-doped Carbon as Peroxidase Mimics for Single-Use Colorimetric Bioassays. J Mater Sci 56:13579–13589

    Article  CAS  Google Scholar 

  • Wei H, Wang E (2013) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes. Chem Soc Rev 42:6060–6093

    Article  CAS  Google Scholar 

  • Wei X, Luo X, Wang H, Gu W, Cai W, Lin Y, Zhu C (2020) Highly-defective Fe-N-C catalysts towards ph-universal oxygen reduction reaction. Appl Catal B Environ 263:118347

    Article  CAS  Google Scholar 

  • Wei H, Gao L, Fan K, Liu J, He J, Qu X, Dong S, Wang E, Yan X (2021) Nanozymes: A Clear Definition with Fuzzy Edges. Nano Today 40:101269

    Article  CAS  Google Scholar 

  • Wu J, Wang X, Wang Q, Lou Z, Li S, Zhu Y, Qin L, Wei H (2019) Nanomaterials with enzyme-like characteristics (nanozymes): next-generation artificial enzymes (II). Chem Soc Rev 48:1004–1076

    Article  CAS  Google Scholar 

  • Xi X, Peng X, Xiong C, Shi D, Zhu J, Wen W, Zhang X, Wang S (2020) Iron Doped Graphitic Carbon Nitride with Peroxidase like Activity for Colorimetric Detection of Sarcosine and Hydrogen Peroxide. Microchim Acta 187:383

    Article  CAS  Google Scholar 

  • Xian J, Weng Y, Guo H, Li Y, Yao B, Weng W (2019) One-pot Fabrication of Fe-doped Carbon Nitride Nanoparticles as Peroxidase Mimetics for H2O2 and Glucose Detection. Spectrochim Acta A Mol Biomol Spectrosc 215:218–234

    Article  CAS  Google Scholar 

  • Yang W, Huang T, Zhao M, Luo F, Weng W, Wei Q, Lin Z, Chen G (2017) High peroxidase-like activity of iron and nitrogen co-doped carbon dots and its application in immunosorbent assay. Talanta 164:1–6

    Article  CAS  Google Scholar 

  • Zhang D, Mao X, ZhangS Z, Zhang S, Chen J, Shan D, Lu X (2019) Fabricated Nanoplatform of Cu(II)-Functionalized Mimetic-peroxidase with Catalytic Property Toward Sensitive Monitoring of Hydrogen Peroxide. Sensors Actuators B Chem 284:684–694

    Article  CAS  Google Scholar 

  • Zhu D, Zhuo S, Zhu C, Zhang P, Shen W (2019) Synthesis of Catalytically Active Peroxidase-like Fe-doped Carbon Dots and Application in Ratiometric Fluorescence Detection of Hydrogen Peroxide and Glucose. Anal Methods 11:2663

    Article  CAS  Google Scholar 

Download references

Funding

This research was supported by a research award to BL and XZ under the NSF EPSCoR award (NSF #1301726). Stephen Spain from the Department of Chemistry at the University of Nevada Reno helped on the collection of EPR data.

Author information

Authors and Affiliations

Authors

Corresponding authors

Correspondence to Bryan Lee or Xiaoshan Zhu.

Ethics declarations

Conflict of interest

The authors declare that they have no conflict of interest.

Additional information

Publisher's note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

Below is the link to the electronic supplementary material.

Supplementary file1 (DOC 6080 KB)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Lee, B., Tian, S., Xiong, G. et al. Solvothermal synthesis of transition metal (iron/copper) and nitrogen co−doped carbon nanomaterials: comparing their peroxidase−like properties. J Nanopart Res 24, 85 (2022). https://doi.org/10.1007/s11051-022-05470-y

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1007/s11051-022-05470-y

Keywords

Navigation