A novel biochar from Ni-fed picochlorum eukaryotum for use as a high-performance enzyme-free electrochemical sensor of hydrogen peroxide

Abstract

A novel method for the preparation of a homogeneous Ni-doped microalgae-based biochar material Ni-f-BC was established by combining biological feed from marine microalgae with soluble nickel salts (at an optimized concentration of 40 mg/L NiCl₂) and successive carbonization with programmed temperature pyrolysis under N₂ flow. A uniform distribution of Ni with an average size of approximately 10 nm was identified by scanning electron microscopy (SEM), scanning transmission electron microscopy (STEM), and energy-dispersive X-ray spectroscopy (EDS) analyses. Successively, a biochar-coated electrode (Ni-f-BC/GCE) was prepared by the ultrasonic dispersion of the biochar in N-methyl-2-pyrrolidone (1 mg/mL) onto a glassy carbon electrode. A sensitive H₂O₂ sensor was developed based on our biochar materials with very good electrochemical performance, namely, with excellent electrocatalytic oxidation ability, a low detection limit of 0.39 μM in the physiological pH range (pH 7–8) and a rapid response time of 2.0 s. Notably, this sensor still exhibited good recovery rates of more than 90%, even in complex environments.

Keywords

Biochar / Ni-doped / Microalgae / H₂O₂ sensor / Electrochemical determination

References

[1] Abdelfattah A, Ali SS, Ramadan Het al.. Microalgae-based wastewater treatment: mechanisms, challenges, recent advances, and future prospects. Env Sci Ecotechnol, 2023, 13 100205

[2] Baek G, Lee J. Algae-derived electrodes in bioelectrochemical systems. J Environ Chem Eng, 2024, 12 112535

[3] Chen S, Xie Y, Guo X et al (2022) Self-supporting electrochemical sensors for monitoring of cell-released H₂O₂ based on metal nanoparticle/MOF nanozymes. Microchem J 181:107715. https://doi.org/10.1016/j.microc.2022.107715

[4] Cheng CF, Zhang CM, Gao XHet al.. 3D network and 2D paper of reduced graphene Oxide/Cu₂O composite for electrochemical sensing of hydrogen peroxide. Anal Chem, 2017, 90: 1983-1991

[5] Darvishmehr Z, Naderi L, Shahrokhian Set al.. Electrodeposition of CoFeS nanoflakes on Cu₂O nanospheres as an ultrasensitive sensing platform for measurement of the hydrazine and hydrogen peroxide in seawater sample. Chemosphere, 2024, 352 141340

[6] Dong K, Liang J, Wang Yet al.. Honeycomb carbon nanofibers: a superhydrophilic O₂-entrapping electrocatalyst enables ultrahigh mass activity for the two-electron oxygen reduction reaction. Angew Chem Int Ed, 2021, 60: 10583-10587

[7] Failla M, Ferlazzo A, Abbate Vet al.. THP as a sensor for the electrochemical detection of H₂O₂. Bioorganic Chem, 2024, 152 107721

[8] Fu X, Liu X, Hao Det al.. Nickel-catcher-doped zwitterionic hydrogel coating on nickel-titanium alloy toward capture and detection of nickel ions. Front Bioeng Biotechnol, 2021, 9 698745

[9] Gan HY, Liang YW, Tang Yet al.. A practical electrochemical method for determining the inhibitory activity of New Delhi Metallo-β-lactamase-1 inhibitors. Microchem J, 2023, 195 109418

[10] Guo Q, Liu Y, Wang Jet al.. Flexible Co-Ni nanocomposites in situ synthesized on carbon fibers for highly sensitive electrochemical detection of H₂O₂. Chin J Anal Chem, 2024, 52 100394

[11] He H, Zhang R, Zhang Pet al.. Functional carbon from nature: biomass-derived carbon materials and the recent progress of their applications. Adv Sci, 2023, 10: 2205557

[12] Huang K, Chang M, Zhang Jet al.. Exploring the impact of Ni doping on Bagasse biochar and its efficient hydrogen production via assisted water electrolysis. Energy Technol, 2023, 11: 2201450

[13] Huo S, Song X, Zhao Yet al.. Insight into the significant contribution of intrinsic carbon defects for the high-performance capacitive desalination of brackish water. J Mater Chem A, 2020, 8: 19927-19937

[14] Jiao L, Xu WQ, Yan HYet al.. Fe-N-C single-atom nanozymes for the intracellular hydrogen peroxide detection. Anal Chem, 2019, 91: 11994-11999

[15] Ju J, Chen W. In situ growth of surfactant-free gold nanoparticles on nitrogen-doped graphene quantum dots for electrochemical detection of hydrogen peroxide in biological environments. Anal Chem, 2015, 87: 1903-1910

[16] Kim S, Kang SC, Lee SMet al.. A novel electrochemical strategy to detect hydrogen peroxide by utilizing peroxidase-mimicking activity of cerium oxide/graphene oxide nanocomposites. Biosens Bioelectron, 2024, 253 116161

[17] Kokulnathan T, Wang TJ, Ahmed Fet al.. Synergism of Holmium orthovanadate/phosphorus-doped carbon nitride nanocomposite: nonenzymatic electrochemical detection of hydrogen peroxide. Inorg Chem, 2024, 63: 3019-3027

[18] Komkova MA, Karyakina EE, Karyakin AA. Catalytically synthesized Prussian blue nanoparticles defeating natural enzyme peroxidase. J Am Chem Soc, 2018, 140: 11302-11307

[19] Lee KS, Park MS, Kim J. Nitrogen doped activated carbon with nickel oxide for high specific capacitance as supercapacitor electrodes. Colloid Surf A-Physicochem Eng Asp, 2017, 533: 323-329

[20] Leng M, Cui Y, Feng Qet al.. In situ monitoring of dynamic H₂O₂ produced upon the external stress of plants using Ag@ZIF-67 based fluorescence sensor. Sens Actuator B-Chem, 2025, 433 137472

[21] Li CX, Zheng Z, Zhou WLet al.. NiFe oxide nanocatalysts grown on carbonized algal cells for enhanced oxygen evolution reaction. J Electrochem Soc, 2018, 165: J3157-J3165

[22] Li GL, Chen Y, Liu Fet al.. Portable visual and electrochemical detection of hydrogen peroxide release from living cells based on dual-functional Pt-Ni hydrogels. Microsyst Nanoeng, 2023, 9: 152

[23] Li YC, Zhong YM, Zhang YYet al.. Carbon quantum dots/octahedral Cu₂O nanocomposites for non-enzymatic glucose and hydrogen peroxide amperometric sensor. Sens Actuator B-Chem, 2015, 206: 735-743

[24] Li YJ, Zhu N, Su ZXet al.. An hourglass-shaped nickel-based polyoxometalate crystalline material as a highly efficient bifunctional electrocatalyst for the oxygen evolution reaction and detection of H₂O₂. Inorg Chem Front, 2024, 11: 2598-2607

[25] Liu J, Liu K, Liu X et al (2025) Self-powered biosensor driven by a hybrid biofuel cell with CuCoP-polyoxometallate composite as both cathode catalyst and sensing interface. Small 21:2500451. https://doi.org/10.1002/smll.202500451

[26] Liu YP, Zhu YX, Chen LQet al.. Ni/WS₂/WC composite nanosheets as an efficient catalyst for photoelectrochemical hydrogen peroxide sensing and hydrogen evolution. Materials, 2024, 17: 1037

[27] Lorencova L, Bertok T, Dosekova Eet al.. Electrochemical performance of Ti₃C₂T_x MXene in aqueous media: towards ultrasensitive H₂O₂ sensing. Electrochim Acta, 2017, 235: 471-479

[28] Lucio-Rivera Z, Gudgel R, Smith Aet al.. Enhancement of H₂O₂ current at electrodes made of fenton-activated carbon nanotubes. J Electroanal Chem, 2024, 956 118094

[29] Ma SY, Xiao SH, Hong YHet al.. Coupling metal organic frameworks nanozyme with carbon nanotubes on the gradient porous hollow fiber membrane for nonenzymatic electrochemical H₂O₂ detection. Anal Chim Acta, 2024, 1293 342285

[30] Maji SK, Sreejith S, Mandal AKet al.. Immobilizing gold nanoparticles in mesoporous silica covered reduced graphene oxide: a hybrid material for cancer cell detection through hydrogen peroxide sensing. ACS Appl Mater Interfaces, 2014, 6: 13648-13656

[31] Nagaraja S, Pelton AR. Corrosion resistance of a nitinol ocular microstent: implications on biocompatibility. J Biomed Mater Res Part B, 2020, 108: 2681-2690

[32] Pimpilova M. A brief review on methods and materials for electrode modification: electroanalytical applications towards biologically relevant compounds. Discover Electrochemistry, 2024, 1: 12

[33] Priyadarshini E, Priyadarshini SS, Pradhan N. Heavy metal resistance in algae and its application for metal nanoparticle synthesis. Appl Microbiol Biotechnol, 2019, 103: 3297-3316

[34] Qiu K, Daoyuan Y, Xiaoyan Zet al.. Survey of six metal contaminants and impurities and eleven metals and alloy components released from stainless-steel sheets on the Chinese market. Food Addit Contam Part A-Chem, 2021, 38: 2091-2101

[35] Ramesh M, Umamatheswari S, Sankar Cet al.. Sonochemical synthesis of Ag-functionalized Fe₂O₃ nanocomposites for the highly sensitive electrochemical detection of ractopamine and H₂O₂. ACS Appl Nano Mater, 2024, 7: 2929-2938

[36] Rashed MA, Rahman MH, Nayem NI et al (2024) Efficient amperometric detection of H₂O₂ using Gold nanoparticle decorated polythiophene/hematite ore nanocomposite. J Electrochem Soc 171. https://doi.org/10.1149/1945-7111/ad2644

[37] Salam KA (2019) Towards sustainable development of microalgal biosorption for treating effluents containing heavy metals. Biofuel Res J 6:948–961. https://doi.org/10.18331/brj2019.6.2.2

[38] Shen H, Liu J, Pan Pet al.. One-step synthesis of nanosilver embedding laser-induced graphene for H₂O₂ sensor. Synth Met, 2023, 293 117235

[39] Shi ZZ, Li YP, Wu XSet al.. Integrated sandwich-paper 3D cell sensing device to in situ wirelessly monitor H₂O₂ released from living cells. Anal Chem, 2024, 96: 3177-3185

[40] Shringi AK, Kumar R, Dennis NFet al.. Two-dimensional tellurium nanosheets for the efficient nonenzymatic electrochemical detection of H₂O₂. Chemosensors, 2024, 12: 17

[41] Siampani M, Lazanas AC, Spyrou Ket al.. Eco-friendly spark-generated Co_xO_y nanoparticle-modified graphite screen-printed sensing surfaces for the determination of H₂O₂ in energy drinks. Microchim Acta, 2024, 191: 150

[42] Song CY, Wang GL, Zhang FFet al.. One-pot synthesis of crossed Fe₂O₃ nanosheets in-situ grown on Ni foam and the application for H₂O₂ electrooxidation. J Alloy Compd, 2020, 817 152770

[43] Su D, Li Q, Liang H et al (2025) A novel electrochemical sensor for real-time quantitative monitoring of neuronal hydrogen peroxide under hypoxic conditions. Chem Eng J 512:162754. https://doi.org/10.1016/j.cej.2025.162754

[44] Sun YM, He K, Zhang ZFet al.. Real-time electrochemical detection of hydrogen peroxide secretion in live cells by Pt nanoparticles decorated graphene–carbon nanotube hybrid paper electrode. Biosens Bioelectron, 2015, 68: 358-364

[45] Suratman A, Astuti DN, Kusumastuti PPet al.. Comprehensive study of thermochemical conversion of biomass okara into biochar. J Anal Appl Pyrolysis, 2024, 181 106594

[46] Tang X, Gao W, Wu ZWet al.. Ni(II) complex based on imidazole dicarboxylic acid as a promising electrocatalyst for hydrogen evolution reaction and H₂O₂-sensing. Electrocatalysis, 2024, 15: 214-225

[47] Xie FY, Cao XQ, Qu FLet al.. Cobalt nitride nanowire array as an efficient electrochemical sensor for glucose and H₂O₂ detection. Sens Actuator B-Chem, 2018, 255: 1254-1261

[48] Yang LZ, Xu CL, Ye WCet al.. An electrochemical sensor for H₂O₂ based on a new Co-metal-organic framework modified electrode. Sens Actuator B-Chem, 2015, 215: 489-496

[49] Zhang J, Jin L, Li Yet al.. Ni doped carbons for hydrogen production by catalytic methane decomposition. Int J Hydrog Energy, 2013, 38: 3937-3947

[50] Zhang XM, Bai MY, Ge Let al.. Electrochemical control of the morphological evolution of PEDOT on a Ni-Co(OH)₂/carbon cloth surface to modulate the performance of wearable H₂O₂ sensors. Nanoscale, 2024, 16: 8162-8176

[51] Zhang YH, Li N, Liu Bet al.. Hydrogen peroxide and dopamine sensors based on electrodeposition of reduced graphene oxide/silver nanoparticles. Sensors, 2024, 24: 355

[52] Zhou M, Catanach J, Gomez Jet al.. Effects of nanoporous carbon derived from microalgae and its CoO composite on capacitance. ACS Appl Mater Interfaces, 2017, 9: 4362-4373

[53] Zuo L, Wang X, Zuo Met al.. Preparation of microalgae-based carbon materials with Ni(OH)₂ doping and their electrochemical performance. J Energy Storage, 2024, 102 114169

Funding

National Natural Science Foundation of China(21702239)

RIGHTS & PERMISSIONS

The Author(s)