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DOI: 10.1039/D5CC03220B (Highlight) Chem. Commun., 2025, Advance Article

Nanozymes in marine antifouling applications: a focus on haloperoxidase activity

Junzhi Yi, Yihe Zhang*, Na Zhang*, Caixia Gao, Shuo Zhao, Jiangbin Zhao, Jing Liu and Ruoyu Jia
Engineering Research Center of Ministry of Education for Geological Carbon Storage and Low Carbon Utilization of Resources, Beijing Key Laboratory of Materials Utilization of Nonmetallic Minerals and Solid Wastes, National Laboratory of Mineral Materials, School of Materials Science and Technology, China University of Geosciences, Beijing, 100083, China. E-mail: zyh@cugb.edu.cn; nazhang@cugb.edu.cn

Received 7th June 2025 , Accepted 7th August 2025

First published on 9th August 2025

Abstract

Marine biofouling is the buildup of microorganisms, plants, and animals on underwater surfaces. It causes major economic and environmental problems. Traditional antifouling methods often use toxic chemicals. These chemicals harm the environment. Recently, nanozymes have become a promising solution. Nanozymes are nanomaterials that act like enzymes. They are stable, have adjustable activity, and are eco-friendly. Some nanozymes exhibit haloperoxidase (HPO) activity. These nanozymes can produce hypohalous acids (HOX), which help prevent fouling. This review covers recent progress in designing and synthesizing HPO-like nanozymes. It focuses on their use in marine antifouling, how they work, their effectiveness, and their environmental safety. The review also suggests future research directions and challenges. The goal is to advance sustainable antifouling technologies.

1. Introduction

Marine biofouling is recognized as a global challenge. Billions of dollars are lost annually due to this issue.1,2 Severe environmental problems are also caused.3,4 Over the past century, antifouling coating technology has been widely studied and used.5 However, traditional antifouling materials in coatings are now known to pose a threat to marine ecosystems.6,7 These materials reduce biofouling but harm the environment.8

New antifouling materials must be developed. These materials should effectively prevent biofouling. Negative impacts on the marine environment should be minimized. Harmony between humans and nature should be achieved. Nanozyme-based solutions are considered promising for future applications.9

In natural ecosystems, a unique chemical defense mechanism against microbial contamination is demonstrated by seaweeds. This mechanism operates through the disruption of bacterial quorum sensing and the regulation of biofilm formation.10,11 Biofilms are capable of secreting an enzyme known as vanadium-dependent haloperoxidase (V-HPO). This enzyme facilitates the reaction between halides and hydrogen peroxide, resulting in the formation of hypohalous acids.12 These acids, including hypochlorous acid and hypobromous acid, are highly damaging to a wide range of organisms, primarily due to their potent bactericidal and oxidative properties. They also effectively inhibit the formation of biofilms. This natural defense mechanism is regarded as a highly promising and environmentally friendly alternative to the currently dominant antibiofouling strategies. Unlike these conventional methods, which are based on the release of toxic heavy metal biocides, the natural approach offers a more sustainable and less harmful solution.13–16 However, the large-scale application of natural enzymes is limited by several challenges. These include difficulties in extraction, issues related to instability, and the need for harsh reaction conditions.17,18 Drawing inspiration from the natural role of vanadium-containing haloperoxidases (V-HPOs) in preventing bacterial biofilm formation on seaweed surfaces,19 both native V-HPOs and their functionally recombinant variants have been extensively utilized as additives in antifouling coatings.20

Nanozymes are described as nanoscale materials that possess catalytic properties similar to those of enzymes.21,22 Specific substrates can be selectively catalyzed by them. Nanozymes are better than natural enzymes in several aspects, including lower production expenses, greater stability, and ease of preparation.23 Superior catalytic performance is also shown by them. In 2007, Yan's team made a groundbreaking discovery that iron oxide nanoparticles (Fe3O4) exhibit intrinsic peroxidase-like activity, which catalyzes the oxidation of substrates such as 2,2′-azino-bis 3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) in the presence of hydrogen peroxide. This finding laid the foundation for the development of Fe3O4 nanoparticles as artificial enzyme mimetics.24 The concept of nanozymes was first proposed. Since then, nanozyme research has expanded. Application in the antibacterial use, pollutant degradation, cancer treatment, and biosensors has been achieved.25,26

In recent years, progress in marine antifouling has been made using nanozymes.27 Their catalytic mechanisms provide innovative solutions to biofouling, especially by mimicking the natural defense systems of marine organisms through haloperoxidase (HPO)-like activity.28–30 Compared with traditional antifouling agents that often rely on toxic heavy metals or biocides, nanozymes offer several compelling advantages. These include high catalytic efficiency under mild conditions, excellent structural and functional stability, and minimal environmental toxicity. In particular, their enzyme-like activity allows for the generation of reactive species that can degrade biofouling organisms without releasing harmful residues. Furthermore, the tunable composition and surface properties of nanozymes enable targeted and sustained antifouling effects, making them a promising class of environmentally friendly antifouling materials. Beyond haloperoxidase mimics, recent studies have highlighted the broader potential of nanozymes including multi-metallic and metal oxide-based systems for antifouling and antibacterial applications. For instance, multi-metallic nanozymes exhibit enhanced catalytic efficiency due to synergistic effects between different metal active sites, enabling robust generation of reactive oxygen species (ROS) under mild conditions.31 In parallel, the use of nanomaterial-enhanced PDMS coatings has emerged as a green antifouling strategy, where incorporation of carbon-based nanomaterials or metal oxides significantly improves mechanical durability, hydrophobicity, and microbial resistance of the coating. These coatings not only resist initial microbial adhesion, but also exhibit long-term antifouling effects via photocatalytic or bactericidal action.32 Furthermore, recent developments in hybrid nanofillers and structural optimization have pushed forward the antifouling performance of these composites under realistic marine conditions.33 These advancements collectively underscore the expanding role of nanozymes and functional nanomaterials in the next generation of sustainable marine antifouling materials.

2. Mechanism of HPO-like nanozymes in marine antibiofouling

The process of marine biofouling is illustrated in Fig. 1. Within minutes of an object coming into contact with seawater, organic molecules (such as proteins and polysaccharides) in the seawater form a conditioning film on the object's surface.34 This film attracts microorganisms (such as bacteria and diatoms) from the seawater,35 which then attach to the surface and form a biofilm. This biofilm provides sites and nutrients for the subsequent attachment of fouling organisms.36 The biofilm reflects the interactions between microorganisms and their surrounding environment and is a key factor in the process of marine biofouling.
image file: d5cc03220b-f1.tif
Fig. 1 The process of marine biofouling.

Quorum sensing (QS)37 is a critical mechanism controlling biofilm formation. QS is a cell-coordination response guided by signaling molecules (autoinducers, AIs) secreted by bacteria. It controls bacterial growth and collective behavior by modulating the synthesis of virulence factors, including toxins and proteases.38 The primary quorum sensing (QS) signaling molecules consist of acyl-homoserine lactones (AHLs, prevalent in Gram-negative bacteria), autoinducing peptides (AIPs, typical in Gram-positive bacteria), and furanosyl borate diester (AI-2, common across diverse bacterial species).11,39,40

The antifouling function of HPO-like nanozymes is achieved through their unique chemical catalytic activity, which inhibits QS and biofilm formation, preventing further development of biofouling.41–43 The mechanism of HPO-like nanozymes relies on their unique catalytic ability. Hypohalous acids with strong antibacterial activity are generated. Bacterial quorum sensing (QS) and biofilm formation are inhibited. This prevents the attachment and reproduction of fouling organisms. For example, studies have shown that HPO-like nanozymes, such as CeO2−x nanorods, can efficiently catalyze bromination reactions. The production of bacterial signaling molecules is blocked.44 Their antibacterial and antifouling performance is comparable to that of immobilized enzymes.

Additionally, HPO-like nanozymes can efficiently brominate quorum sensing signaling molecules. Highly reactive antibacterial intermediates are also produced. As a result, high stability and long-lasting effectiveness are demonstrated in practical applications.45

When nanomaterials exhibit HPO (haloperoxidase) catalytic activity, they essentially function as enzymes that catalyze the halogenation and oxidation reactions of substrates.46 The specific reaction mechanism for Fe3O4 nanoparticles, which exhibit peroxidase-like activity, can be summarized as follows:

(a) In the presence of organic acceptors, highly reactive intermediate species, such as hypohalous acids, are generated under the catalysis of HPO enzymes.47 These intermediates subsequently undergo reactions with a variety of nucleophilic acceptors (R–H), leading to the formation of halogenated metabolic compounds (eqn (1.1) and (1.2)). In cases where the nucleophilic acceptor comprises amino groups, the resulting products are haloamines (eqn (1.3)).48

 
image file: d5cc03220b-t1.tif(1.1)
 
image file: d5cc03220b-t2.tif(1.2)
 
R2NH + HOX → R2NH + H2O (1.3)

(b) In the absence of organic acceptors, particularly under basic conditions with elevated hydrogen peroxide (H2O2) levels, HPO produces singlet oxygen (1O2) through a perhalogenated halide intermediate (eqn (1.4)).

 
image file: d5cc03220b-t3.tif(1.4)

Highly reactive intermediates, such as hypohalous acids (HOX), haloamines (R2NX), and reactive oxygen species like singlet oxygen (1O2), are involved in processes of oxidative halogenation. These reactions target nucleophilic compounds, inactivated substrates, and even simpler chemical species.49 HPO has been identified as an important biocatalyst in processes such as natural product precursor generation, metabolic reactions, and selective oxidation. HPO is involved in the biosynthesis of natural products, including halogenated metabolites, terpenes, indoles, phenols, and other compounds derived from amino acids.50–52 Halogenase-catalyzed reactions are widespread in marine organisms. Research by the Tremel group demonstrated that V2O5 nanowires can oxidize Br− to produce HOBr and 1O2 in a system containing 10 μM H2O2 and 1 mM Br−, with the latter exhibiting strong antibacterial activity.53 Subsequently, the same group found that CeO2−x nanorods also possess HPO activity. In a system containing 0.3 μM hydrogen peroxide (H2O2) and 0.25 mM bromide ions (Br−), the bromination of the signaling molecule N-(3-oxoacyl) homoserine lactone was efficiently catalyzed. The catalytic efficiency achieved was on par with that of immobilized enzymes, and it effectively disrupted bacterial quorum sensing.44 The use of HPO-mimicking nanozymes as biofilm inhibitors in marine antifouling represents a novel strategy aimed at mimicking the natural defense systems of marine organisms to prevent bacterial colonization or biofilm development, thereby controlling biofouling.

3. Wild-type vanadium haloperoxidases (VHPOs)

Haloperoxidase (HPO) is an enzyme that functions as a halogenase, participating in halogenation reactions.54 In 1959, Hager et al.55 discovered it in Fungus calderiomyces fumago while investigating the natural biosynthetic sources of caldariomycin. It is widely distributed in nature. Haloperoxidases are categorized according to the halogen ions they act upon, namely chloroperoxidase, bromoperoxidase, and iodoperoxidase. These classifications reflect the varying affinities of these enzymes for different halogens. Additionally, based on their prosthetic groups, haloperoxidases are further classified into ferriprotoporphyrin-containing enzymes,56–58 vanadium-dependent enzymes,59–61 and those that lack a prosthetic group.62 Among them, vanadium haloperoxidase has been the most extensively studied.63 Vanadium haloperoxidases (VHPOs) are naturally occurring metalloenzymes found in marine algae, fungi, and certain bacteria. The active site features a vanadium (V) center coordinated by oxo and hydroxo ligands in a distorted trigonal bipyramidal geometry (Fig. 2a) Upon reacting with H2O2, a peroxovanadate intermediate is formed and facilitates electrophilic halide oxidation to generate hypohalous acid.64 The catalytic cycle efficiently regenerates the vanadium center for continuous turnover (Fig. 2b). These enzymes have received increasing attention due to their relevance in marine halogen cycles and their role in producing antimicrobial agents such as HOBr and singlet oxygen (1O2). High-resolution crystallographic studies have shown that the vanadate cofactor is stabilized by conserved residues such as histidine, arginine, and aspartate, which are critical to activity and substrate binding.65,66 These biological insights have laid the foundation for the rational design of biomimetic haloperoxidase-like nanozymes.
image file: d5cc03220b-f2.tif
Fig. 2 (a) The vanadium site of V-BrPO (A. nodosum). (b) Proposed reaction scheme for V-BrPO catalysis.67 Copyright 2004. Royal Society of Chemistry.

Over the past few decades, increasing attention has been paid to the problem of marine biofouling.68 Researchers have been searching for effective and environmentally friendly solutions. In this context, HPO-like nanozymes have become an ideal choice for mimicking vanadium-dependent haloperoxidases (V-HPOs) found in nature. These nanozymes facilitate the oxidation of halide ions under moderate conditions. Hypobromous acid (HOBr) and singlet oxygen (1O2) are generated. Both have strong oxidative and antimicrobial properties. This effectively prevents the formation of microbial biofilms on surfaces.69

4. Main types of HPO-like nanozymes

In recent years, HPO-like nanozymes have gained significant attention as innovative biomimetic catalysts capable of replicating the enzymatic functions of natural vanadium-dependent haloperoxidases (V-HPOs). These artificial catalysts offer several advantages, such as enhanced durability, adaptable catalytic performance, and friendliness, positioning them as effective solutions for combating marine biofouling and addressing other industrial issues. Depending on their structural composition, HPO-like nanozymes are broadly classified into vanadium-based, cerium-based, molybdenum-based, single-atom, and sulfide-based variants (Table 1). Each type demonstrates distinct characteristics and practical uses.63,70,71 In this review, we highlight HPO-like nanozymes that exhibit superior performance and discuss their applications based on the variety of metal atoms they incorporate.
Table 1 Typical halogenated peroxide nanozymes
Main classification Materials Substrate Km (M) Ref.
Natural haloperoxidase A haloperoxidase from Curvularia inaequalis H2O2 1.6 × 10−4 109
Br− 3.1 × 10−3
A haloperoxidase from Ascophyllum nodosum H2O2 2.2 × 10−4 110
Br− 1.81 × 10−2
Vanadium-based HPO-like nanozymes V2O5 nanowires H2O2 1 × 10−5 53
Br− —
CeO2@C H2O2 2 × 10−3 87
Br− 0.5
Cerium-based HPO-Like nanozymes CeO2@ZrO2 H2O2 1.02 × 10−4 111
Br− 2.2 × 10−2
CeO2−x nanorods H2O2 2.61 × 10−4 44
Br− 0.35
Ce-400 H2O2 9.25 × 10−2 112
Br− 2.6 × 10−2
Ce-Com H2O2 8.922 × 10−2
Br− 2.3 × 10−2
Ce-Rod H2O2 0.221
Br− 0.5 × 10−2
Molybdenum-based HPO-like nanozymes Ni16Mo16P24 H2O2 1.143 × 10−4 92
Br− 2.772 × 10−5
PMo12 H2O2 0.79 × 10−3 91
Br− 0.92 × 10−3
Ov-PMo12 H2O2 0.66 × 10−3
Br− 0.49 × 10−3
Single-atom HPO-like nanozymes MVCM H2O2 1.0 × 10−4 100
Br− 0.22
Mo SA-N/C H2O2 2.193 × 10−4 102
Br− 9.9 × 10−3
W-UiO H2O2 5.55 × 10−4 113
Br− 0.119
Cr-SA-CN H2O2 2.2 × 10−5 101
Br− 1.81 × 10−2
MoS2 H2O2 4.58 × 10−4 107
Br− 0.184
Co-MoS2 H2O2 1.17 × 10−4
Br− 0.028
Sulfide-based HPO-like nanozymes Ni-MoS2 H2O2 2.48 × 10−4 108
Br− 0.06
Zn-MoS2 H2O2 6.23 × 10−4
Br− 0.227
NiMoS2 H2O2 2.503 × 10−4
Br− 0.017
L-NiMoS2 H2O2 1.858 × 10−4
Br− 9.6 × 10−3

4.1. Vanadium-based HPO-like nanozymes

Vanadium-based nanozymes (HPO-like) are materials that mimic the activity of natural vanadium-dependent haloperoxidases (V-HPOs). These materials are usually found as vanadium oxides or sulfides. They facilitate the conversion of halide ions into hypohalous acids through an oxidation process. This activity shows strong antibacterial and anti-biofouling properties. In fields like seawater desalination and wastewater treatment, vanadium-based HPO-like nanozymes are highly valued for their photothermal conversion efficiency and HPO-like activity.72,73

In 1996, Colpas et al.74 first described the synthesis and reaction mechanisms of vanadium-based complexes as models for V-HPOs. This work laid the foundation for future research. Later, in 2012, Natalio et al.53 demonstrated the potential of vanadium pentoxide (V2O5) nanowires in mimicking V-HPO activity (Fig. 3a). These nanowires were discovered to efficiently catalyze the conversion of bromide ions, generating bromine-based oxidants and reactive oxygen species. They also showed high stability and activity under both laboratory and seawater conditions (pH = 8.3). Importantly, when used in antifouling coatings (Fig. 3(b–d)), these nanowires prevented biofouling on surfaces for up to 60 days in seawater. Their toxicity to marine organisms was much lower than that of antifouling products approved by the International Maritime Organization (IMO). This makes them a promising environmentally friendly antifouling agent.


image file: d5cc03220b-f3.tif
Fig. 3 (a) Illustration of the antimicrobial mechanism of V2O5/coating nanocomposites. (b) Evaluation of antimicrobial properties of V2O5/coating nanocomposites. (c) Representative images showing bacterial growth of S. aureus and E. coli with and without active V2O5 nanowires. (d) Photographs comparing a stainless steel panel coated with marine paint in the presence (+V2O5 nw) and absence (−V2O5 nw) of V2O5 nanowires.53 Copyright 2012. Springer Nature Limited.

4.2. Cerium-based HPO-like nanozymes

Cerium-based nanozymes are emerging catalytic materials that show great potential, thanks to their distinctive electronic properties, chemical stability, and catalytic activity.75–82 They are particularly effective in mimicking the activity of natural haloperoxidases (HPOs). Cerium oxide (CeO2) and its nanostructures can catalyze the oxidation of halide ions under mild conditions, generating highly oxidative species such as hypobromous acid (HOBr) and singlet oxygen (1O2). These reactive species exhibit strong antibacterial and anti-biofilm formation properties.83 As a result, cerium oxide-based nanozymes offer new solutions for marine biofouling prevention, demonstrating more efficient performance in preventing microbial colonization and biofilm formation compared to traditional methods.

In 2021, Wu et al.84 reported a method for synthesizing defective cerium oxide through room-temperature self-assembly. Defective cerium oxide is characterized by abundant oxygen vacancies, which enhance its haloperoxidase-like activity in catalytic oxidation reactions compared to traditional cerium oxide. When in contact with marine substrates, cerium oxide, which features numerous oxygen vacancies, demonstrated strong catalytic performance in converting bromide ions into hypobromous acid (Fig. 4a). This material also showed strong antibacterial effects against both Gram-positive Staphylococcus aureus and Gram-negative Escherichia coli (Fig. 4b). Compared to traditional cerium oxide materials, defective cerium oxide exhibited higher stability in marine environments, maintaining its antifouling performance over extended periods. In open seawater, coatings containing defective cerium oxide showed significant antifouling performance for up to 60 days (Fig. 4c), indicating broad application prospects.


image file: d5cc03220b-f4.tif
Fig. 4 (a) Illustration of oxidative bromination and UV–Vis spectra. (b) Images comparing E. coli and S. aureus. (c) Stainless steel plates with various paints, before/after ocean immersion.84 Copyright 2021. Springer Nature Switzerland AG.

In 2022, Phil Opitz et al.85 demonstrated that lanthanide (Ln) substitution in Ce1−xLnxO2−x/2 significantly enhances the haloperoxidase-like activity of nano-ceria. Non-agglomerated nanoscale Ce1−xLnxO2−x/2 was prepared via a mechanochemical method from CeCl3 and Na2CO3 (Fig. 5a), followed by short-term calcination. The arrangement of Ln3+ sites in the CeO2 framework, which becomes more prevalent at higher dopant concentrations, was analyzed using electron spin resonance (ESR) spectroscopy (Fig. 5b). Ce3+ and superoxide species (O2−) were identified at the surface. Vibrational spectroscopy (Fig. 5c) revealed the surface defect chemistry of Ce1−xLnxO2−x/2, which is associated with the mechanochemical synthesis and promotes superior catalytic performance. Despite a reduced BET surface area relative to pure CeO2 (Fig. 5d and e) Ce0.9Pr0.1O1.95 exhibited significantly higher catalytic activity in the oxidative bromination of phenol red. This phenomenon can be attributed to the significant enhancement in the ζ-potential, which escalates from 15 mV for pure CeO2 to 30 mV for the Ce0.9Pr0.1O1.95 variant. This considerable increase in the ζ-potential markedly bolsters the adsorption efficacy of Br− ions in aqueous settings. Consequently, such enhanced adsorption properties are instrumental in elucidating the exceptional catalytic efficiency demonstrated by Ln-substituted CeO2. Rare earth-doped cerium oxide not only improved catalytic activity but also demonstrated superior performance in preventing marine biofouling compared to traditional materials (Fig. 5f), providing new insights for developing efficient and environmentally friendly antifouling coatings.


image file: d5cc03220b-f5.tif
Fig. 5 (a) TEM of Tb3+ and Pr3+ doped nanoparticles. (b) ESR spectra of CeO2 samples. (c) ESR spectra and simulations for Pr-doped CeO2. (d) BET and turnover rate correlation. (e) ζ-potential and turnover rate correlation. (f) Biofilm formation with various nanocrystals assessed by staining.85 Copyright 2022. Royal Society of Chemistry.

In 2023, Yang et al.86 developed CeO2-DNH by incorporating CeO2 nanorods into a polyzwitterionic hydrogel via a one-step method. The hydrogel features a chemically cross-linked hard network and a physically cross-linked polyvinyl alcohol (PVA) soft network (Fig. 6a). This design combines the catalytic activity of CeO2 nanorods with the anti-adhesive properties of poly (PSBMA-AAm), creating a synergistic effect. The CeO2-DNH hydrogel not only provides excellent antibacterial properties (Fig. 6b) but also effectively prevents microbial attachment and biofilm formation. In real marine environments, the CeO2-DNH hydrogel maintained outstanding antifouling performance for up to six months (Fig. 6c), particularly in terms of anti-adhesion and hydration properties, demonstrating long-term antifouling capabilities. The preparation method for this hydrogel is simple and cost-effective, effectively integrating the catalytic properties of CeO2 nanorods with the anti-fouling functions of polymers. This material shows strong application potential, especially for use on ship hull and other surfaces requiring antifouling protection.


image file: d5cc03220b-f6.tif
Fig. 6 (a) Combined anti-biofouling effects and dual-network architecture of CeO2-DNH hydrogel. (b) Antibacterial efficacy of CeO2 nanoparticles with distinct morphologies. (c) Hydrogel assessment post-6-month sea test with quantified fouling coverage.86 Copyright 2023. American Chemical Society.

In 2024, Zhao et al.87 successfully synthesized an effective haloperoxidase-like enzyme mimic, CeO2@C, with a core–shell structure. Carbon spheres were used as templates, and a simple precipitation method was employed. CeO2@C was shown to have an intrinsic haloperoxidase-like nature through its ability to catalyze the bromination of organic signal compounds, as measured by UV-Vis absorption spectroscopy and kinetic studies (Fig. 7a). The CeO2@C catalyst demonstrated high catalytic stability and recyclability, maintaining excellent performance over at least 10 cycles of substrate renewal (Fig. 7b). This catalyst facilitated the reaction between H2O2 and Br− to generate hypobromous acid, which exhibited potent microbicidal activity against both Gram-negative bacteria and Gram-positive bacteria, as well as typical marine bacteria such as Pseudomonas aeruginosa (Fig. 7c). With its excellent catalytic activity and antibacterial performance, CeO2@C demonstrates great potential for use in environmentally friendly antifouling technology.


image file: d5cc03220b-f7.tif
Fig. 7 (a) Mechanism of CeO2@C mimicking haloperoxidase activity. (b) Reusability of CeO2@C catalyst over multiple cycles. (c) Live/dead stains of three bacteria on bare and CeO2@C titanium plates.87 Copyright 2020. Elsevier B.V.

Research studies into cerium oxide nanozymes in the field of antifouling have been progressively advancing. Their ability to mimic haloperoxidase (HPO) activity has shown significant application potential. Innovations such as enhancing catalytic activity through rare earth doping, leveraging synergistic effects in hydrogel-loaded systems, utilizing the high efficiency of defective cerium oxide, and developing core–shell structured CeO2@C nanoparticles have provided a solid theoretical foundation and practical experience for creating effective and eco-friendly antifouling materials. With continuous advancements in materials science and nanotechnology, cerium-based nanozymes are seen as likely to have a rising influence in future antifouling technologies, offering more sustainable solutions to address marine biofouling.

4.3. Molybdenum-based HPO-like nanozymes

Molybdenum-based nanozymes have been the focus of extensive research, as they exhibit high catalytic activity in redox reactions. In simulating haloperoxidase (HPO) activity, molybdenum-based materials have shown excellent performance. They can effectively catalyze the oxidation of halide ions, generating halide acids with antibacterial properties.88–90 These nanozymes have potential applications in industrial water treatment and medical disinfection.

In 2024, Sun et al.91 developed a functional POM possessing abundant oxygen vacancies. This compound demonstrated both haloperoxidase-like activity and photocatalytic H2O2 generation. Theoretical analysis illustrated that oxygen vacancies boosted the d-band center, consequently fortifying the adsorption of H2O2 and Br− and heightening haloperoxidase-like activity (Fig. 8a–c). The POM compound demonstrates robust H2O2 generation (1.77 mmol h−1 g−1) through enhanced electron–hole pair separation driven by oxygen vacancies. This intrinsic property enables haloperoxidase mimicry for biofouling prevention, eliminating the requirement for exogenous H2O2. The POM compound manifested impressive antibacterial effects against Escherichia coli and Staphylococcus aureus under visible light irradiation in the simulated biofouling experiments. This research revealed the connection between the structure of haloperoxidase imitation and the activity of photocatalytic H2O2 generation, revealing the critical role of oxygen vacancies in enhancing electron–hole separation. These results provide an efficient and environmentally friendly method for biofouling prevention.


image file: d5cc03220b-f8.tif
Fig. 8 (a) Ov-PMo12 combines enzyme mimicry and H2O2 production for antibiofouling. (b) Ov-PMo12 converts PR to Br4PR via HOBr. (c) Structural basis of PMo12: fundamental unit, [PMo12O40]3− cluster, and chain-like arrangement.91 Copyright 2024. Elsevier B.V.

In 2024, Bian Y et al.92 synthesized a wheel-like POM Ni16Mo16P24, which functions as an artificial nanozyme with significant haloperoxidase-like activity. During the electrocatalytic oxygen reduction reaction (ORR) in a neutral electrolyte, it exhibits typical two-electron behavior, yielding H2O2 under specific conditions, respectively. These findings highlight its potential for catalytic applications. Using the electrocatalytically generated H2O2, Ni16Mo16P24 accelerated the conversion of Br− to HOBr, achieving an antibacterial and antifouling strategy without the need for additional H2O2 (Fig. 9a–c). For the bifunctional Ni16Mo16P24, the relationship between its structure and activity was elucidated, including haloperoxidase-like activity and electrocatalytic H2O2 production performance. Importantly, this work proposed an environmentally friendly antibacterial strategy.


image file: d5cc03220b-f9.tif
Fig. 9 (a) Ni16Mo16P24 enables H2O2-free antibiofouling via enzyme mimicry and electrocatalysis. (b) Structural features of Ni16Mo16P24:Ni4P3 and Mo4P7 units, one-dimensional chain-like structure (side and top views), and wheel-like cluster [(Mo4O8)4Ni16O4(H2O)14(HPO4)2(PO4)22] (ball-stick and polyhedron modes). (c) Ni16Mo16P24 converts PR to Br4PR via HOBr.92 Copyright 2024. Royal Society of Chemistry.

4.4. Single-atom HPO-like nanozymes

Single-atom catalysts (SACs) consist of isolated metal atoms on a support. They exhibit significant advantages in catalytic reactions due to their excellent atomic utilization, unique electronic effects, and high activity and selectivity.93–97 In simulating haloperoxidase (HPO) activity, SACs have attracted considerable attention from researchers because they can efficiently catalyze oxidation reactions, generating highly oxidative species such as hypobromous acid (HOBr) and singlet oxygen (1O2). These properties offer potential environmental and biomedical applications.105

With the rapid development of nanoscience and biomimetics, SACs have shown great potential in mimicking the activity of natural enzymes, particularly haloperoxidases.98 These materials are especially significant in the development of marine antifouling technologies and highly sensitive sensors.99

In 2021, Wang et al.100 synthesized MVCM by partially oxidizing a Ce-MOF precursor. The material demonstrated haloperoxidase-like activity, allowing for the oxidative bromination of PR to bromophenol blue when H2O2 and Br− were present (Fig. 10a). Based on this specific chromogenic substrate, a radiometric optical sensing platform was constructed by monitoring the absorbance at 590 nm and 430 nm of the MVCM (PR, Br−) system. This platform enabled highly sensitive detection of H2O2 with a detection limit of 3.25 μM (Fig. 10b and c). Additionally, researchers have proposed that MVCM functions via a haloperoxidase-like mechanism. Enzyme kinetic monitoring revealed that the Km values of MVCM for H2O2 and NH4Br were lower than those of cerium oxide nanomaterials, indicating higher binding affinity of MVCM for H2O2 and NH4Br compared to others. The successful application of cerium-based single-atom catalysts not only provides strong support for HPO activity mimicry but also offers a theoretical basis for developing efficient and environmentally friendly sensors and antifouling technologies. This research breaks through the limitations of traditional catalysts, making catalytic processes more efficient and precise.


image file: d5cc03220b-f10.tif
Fig. 10 (a) Synthesis and application of MVCM nanozyme for ratiometric colorimetric H2O2 detection. (b) Absorption spectra of reaction systems with photos. (c) XRD patterns and XPS spectra of MVCM (Ce 3d and O 1s).100 Copyright 2021. MDPI.

In 2022, Luo et al.101 developed a semiconductor nanozyme constructed from carbon–nitrogen-coordinated chromium single atoms (Cr-SA-CN). This nanozyme exhibits dual functionalities: non-sacrificial H2O2 photosynthesis and haloperoxidase-like antifouling activity. Under visible light irradiation, Cr-SA-CN can generate H2O2 from water and O2, which is then continuously supplied for haloperoxidase-like reactions (Fig. 11a). The dual-active Cr-SA-CN is capable of overcoming the H2O2 dilemma by continuously producing hypobromous acid, demonstrating significant antibacterial capabilities. When used as an environmentally friendly coating additive, Cr-SA-CN successfully prevented marine biofouling by rendering surfaces inert (Fig. 11b). This study not only elucidates an attractive strategy for antibacterial remediation but also opens a new pathway for constructing multifunctional nano-platforms that leverage the advantages of photocatalytic reactions, providing new insights for marine antifouling. This material not only exhibits excellent catalytic activity but also maintains its catalytic effects under environmentally friendly conditions for extended periods, showing significant application potential.


image file: d5cc03220b-f11.tif
Fig. 11 (a) Cr-SA-CN nanozyme: H2O2 generation and bromide oxidation. (b) Display of catalytic antibacterial performance and application in the actual marine environment.101 Copyright 2022. Wiley-VCH GmbH.

In 2022, Wang et al.102 developed a photothermal nanozyme (Mo SA-N/C) with haloperoxidase (HPO)-like activity, utilizing molybdenum single atoms (Mo SA) as active sites. This work highlights the potential of Mo SA-N/C for advanced applications in biofouling control and antibacterial processes. As a functional mimic, this nanozyme can generate cytotoxic hypohalous acids from halides and hydrogen peroxide, similar to natural haloperoxidases. It demonstrates great potential as a novel environmentally friendly anti-biofouling material, effectively inhibiting biofilm formation. DFT calculations revealed that hydroxyl radicals (˙OH) generated from H2O2 dissociation are key intermediates in the formation of hypobromous acid (Fig. 12a). When exposed to light, Mo SA-N/C produces heat and remarkably enhances reaction rates. The study exhibited that Mo SA-N/C has significant broad-spectrum antibacterial efficacy and can act as a top-notch coating additive to restrain biofouling in actual marine scenarios. This work highlights the potential of Mo SA-N/C for antibiofouling applications in marine environments (Fig. 12b). This study into Mo SA-N/C nanozyme demonstrates its potential as a biocompatible and photoresponsive artificial enzyme for combating marine biofouling. The study exhibits that Mo SA-N/C can be employed as an efficient coating additive to suppress biofouling under true marine conditions.


image file: d5cc03220b-f12.tif
Fig. 12 (a) Mo-SA-CN: photocatalytic H2O2 production and in situ bromide oxidation, haloperoxidase-like. (b) Display of Catalytic Antibacterial Performance and Application in the Actual Marine Environment.102 Copyright 2022. Wiley-VCH GmbH.

4.5. Sulfide-based HPO-like nanozymes

Transition metal dichalcogenides (TMDs) have emerged as promising nanomaterials for mimicking the activity of natural haloperoxidases (HPOs) due to their excellent catalytic properties, structural stability, and tunable electronic characteristics. Among these materials, molybdenum disulfide (MoS2) and its derivatives have attracted significant attention.103 Remarkable progress has been achieved in HPO-like activity simulations, primarily attributed to their high chemical stability and abundant surface-active sites. Furthermore, their potential has been demonstrated in antibacterial and anti-biofouling applications.

Molybdenum disulfide (MoS2), a representative TMD, possesses a two-dimensional layered structure. The weak van der Waals forces between layers provide a high surface area and superior electronic conductivity, which establishes MoS2 as an efficient catalytic platform.104–106 In HPO-mimicking systems, the oxidation of halide ions is catalytically promoted by MoS2, resulting in the generation of hypobromous acid (HOBr) and singlet oxygen (1O2). These highly oxidative species are effective in microbial growth inhibition and biofilm formation prevention. Consequently, MoS2 based materials are considered ideal candidates for marine anti-fouling and other fields requiring dual functionality of catalysis and antimicrobial activity.

In 2022, Luo et al.107 enabled the less active MoS2 to display effective haloperoxidase mimetic activity through transition metal engineering by mimicking the natural haloperoxidase defence mechanism against biofilm colonization in algae. Cobalt-doped MoS2 (Co-MoS2) showed excellent haloperoxidase mimicry performance in catalyzing the oxidation of Br- to bactericidal HOBr, which was approximately 2 and 23 times higher than that of nickel-doped MoS2 and pristine MoS2, respectively (Fig. 13a). Thus, Co-MoS2 demonstrated exceptional resistance to bacterial colonization and biofouling in real field tests conducted in the marine environment (Fig. 13b and c). The achievement of robust haloperoxidase-mimetic activity in MoS2 via metal engineering highlights a novel approach for designing highly active transition metal disulfide compounds, potentially revolutionizing antimicrobial and anti-biofouling applications.


image file: d5cc03220b-f13.tif
Fig. 13 (a) Kinetic analysis of phenol red bromination with H2O2 and Br−. (b) Antibacterial efficacy of model bacteria. (c) Coating performance of painted panels with/without nanozyme additives (blank, pristine MoS2, Co–MoS2).107 Copyright 2022. American Chemical Society.

To further enhance the catalytic performance, in 2023, the researchers108 also explored the synthesis of nickel–molybdenum bimetallic sulphide (L-NiMoS2) and its applications (Fig. 14a). By means of nanosecond pulsed laser irradiation and high-temperature treatment, the L-NiMoS2 material exhibited higher active site exposure and improved textural properties, and the catalytic kinetic rate of L-NiMoS2 was enhanced by a factor of 2.6 and 135.7, respectively, in comparison with pristine NiMoS2 and MoS2. The enhanced catalytic activity resulted in a substantial increase in the antimicrobial and anti-pollution capabilities of L-NiMoS2 in the marine environment, especially in mimicking the activity of HPOs, where the generation of hypobromous acid (HOBr) and singly-linear oxygen (1O2) showed significant inhibition of microorganisms (Fig. 14b and c). These studies indicate that nickel–molybdenum bimetallic sulphides have promising applications in biomedical applications and environmental treatment.


image file: d5cc03220b-f14.tif
Fig. 14 (a) Synthesis of L-NiMoS2. (b) Disinfection efficiency and bacterial images. (c), Coating performance with/without nanozyme additives.108 Copyright 2023. Springer Nature Switzerland AG.

5. Challenges and future directions

Nanozymes, as nanomaterials with enzyme-like catalytic activity, exhibit efficient and broad-spectrum properties in the antibacterial field. The antifouling effect is achieved by destroying bacterial biofilm components by catalyzing the generation of strongly oxidizing reactive oxygen radicals and interfering with the population sensing system important for bacterial survival by generating hypohalous acids. Although nanozymes have shown good antifouling properties in laboratory studies, they still face many challenges in practical applications:

(1) High production cost: currently, the production cost of nanozymes is high, which limits their large-scale application. Reducing the cost is the key to achieve its wide application.

(2) Low stability: the stability of nanozymes is relatively low, especially under different environmental conditions, and their catalytic activity may be affected. Improving their stability is key to ensuring their effective work in complex environments.

(3) Insufficient catalytic activity and selectivity: although the catalytic activity of some nanozymes is similar to or even higher than that of natural enzymes, the catalytic activity of most nanozymes is still much lower than that of the corresponding natural enzymes. In addition, nanozymes suffer from poor substrate selectivity. Optimizing their catalytic properties is the key to improving their practical application.

(4) Toxicity issues: the potential toxicity of nanozymes in environmental protection and antimicrobial applications remains a concern. Further studies on their safety are needed to ensure their safety in practical applications.

In the future, research studies should focus on the following priorities to accelerate the practical translation of nanozyme-based antifouling strategies:

(1) Scalability and economic feasibility: design simplified and scalable synthesis routes (e.g., green chemistry, self-assembly, or bioinspired methods) to reduce production costs while maintaining high catalytic activity.

(2) Long-term operational stability: investigate nanozyme stability and reusability under real-world conditions (e.g., salinity, temperature fluctuation, and organic fouling), and develop surface modification strategies to enhance environmental tolerance.

(3) Mechanistic insight and rational design: employ techniques such as molecular dynamics simulations, in situ spectroscopy, and structural analysis to elucidate the catalytic mechanisms and active sites, guiding the design of more efficient and selective nanozymes.

(4) Ecological impact assessment: systematically assess the biocompatibility, degradation pathways, and ecological risks of nanozymes, including their effects on marine microorganisms and food webs.

(5) Expanding application scenarios: beyond marine antifouling, explore the multifunctional potential of haloperoxidase-mimicking nanozymes in biomedical disinfection, water treatment, and smart surface engineering.

In conclusion, haloperoxidases and their nanozyme mimics possess significant promise for sustainable and non-toxic antifouling applications. Through interdisciplinary research combining materials science, catalysis, environmental toxicology, and marine engineering, it will be possible to overcome current limitations and advance the practical deployment of nanozyme-based solutions in real-world settings.

Author contributions

The manuscript was written through contributions of all authors. All authors have given approval to the final version of the manuscript.

Conflicts of interest

There are no conflicts to declare.

Data availability

No primary research result, software or code have been included and no new data were generated or analyzed as part of this Feature Article.

Acknowledgements

This work was supported by the Xiong’an New Area Science and Technology Innovation Special Program [2023XAGG0068].

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