Room temperature synthesis of defective cerium oxide for efficient marine anti-biofouling

Wu, Ronggen; Wang, Wei; Luo, Qi; Zeng, Xiangyang; Li, Jinyang; Li, Yilan; Li, Yunhong; Li, Jianbao; Wang, Ning

doi:10.1007/s42114-021-00256-7

Cited by 10 publications

(7 citation statements)

References 46 publications

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“…The CeO 2−x nanoparticle (NP) coating did not actively inhibit fouling or change fouling community composition compared with the uncoated control. This contrasted with Herget et al 68 and Wu et al 93 who demonstrated beneficial antifouling of stainless-steel plates coated with CeO 2−x NP in freshwater and seawater environments. The enzymatic activity of the CeO 2−x nanoparticles (NPs) catalyzes the oxidation of halides in presence of hydrogen peroxide (H 2 O 2 ) to hypohalous acids (HOX) according to: Br - + H 2 O 2 → HOBr + H 2 O. HOX can react in follow-up reactions to halogenated organic compounds.…”

Section: Discussionmentioning

confidence: 61%

“…Furthermore, the concentration of NPs in our coating could have been too low for the expected antifouling activity and future approaches could test for different NP concentrations in the coatings. Although several studies report substantial reductions in bacterial adhesion 68 , 93 – 95 , literature on suppressed macrofouling species in natural seawater is very scarce 96 . Interestingly, Xu et al 97 reported increased biofilm formation and growth of bacterial strains from wastewater treatment plants at CeO 2−x NP concentrations < 4 mg/L, whereas the opposite effect was observed at CeO 2−x NP concentrations higher than 10 mg/L.…”

Section: Discussionmentioning

confidence: 99%

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Antifouling coatings can reduce algal growth while preserving coral settlement

Roepke

Brefeld

Soltmann

et al. 2022

Sci Rep

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In the early stages after larval settlement, coral spat can be rapidly overgrown and outcompeted by algae, reducing overall survival for coral reef replenishment and supply for restoration programs. Here we investigated three antifouling (AF) coatings for their ability to inhibit algal fouling on coral settlement plugs, a commonly-used restoration substrate. Plugs were either fully or partially coated with the AF coatings and incubated in mesocosm systems with partial recirculation for 37 days to track fouling succession. In addition, settlement of Acropora tenuis larvae was measured to determine whether AF coatings were a settlement deterrent. Uncoated control plugs became heavily fouled, yielding only 4–8% bare substrate on upper surfaces after 37 days. During this period, an encapsulated dichlorooctylisothiazolinone (DCOIT)-coating was most effective in reducing fouling, yielding 61–63% bare substrate. Antiadhesive and cerium dioxide (CeO2−x) nanoparticle (NP) coatings were less effective, yielding 11–17% and 2% bare substrate, respectively. Average settlement of A. tenuis larvae on the three types of AF-coated plugs did not statistically differ from settlement on uncoated controls. However, settlement on the NP-coating was generally the highest and was significantly higher than settlement found on the antiadhesive- and DCOIT-coating. Furthermore, on plugs only partially-covered with AF coatings, larval settlement on coated NP- areas was significantly higher than settlement on coated antiadhesive- and DCOIT-areas. These results demonstrate that AF coatings can reduce fouling intensity on biologically-relevant timescales while preserving robust levels of coral settlement. This represents an important step towards reducing fine-scale competition with benthic fouling organisms in coral breeding and propagation.

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Section: Discussionmentioning

confidence: 61%

Section: Discussionmentioning

confidence: 99%

Antifouling coatings can reduce algal growth while preserving coral settlement

Roepke

Brefeld

Soltmann

et al. 2022

Sci Rep

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“…Next, we explored the HPO‐mimic activity of Mo SA‐N/C using a phenol red bromination assay in an aqueous solution at 25 ± 2 °C. [ 45 ] The time‐dependent absorbance increase of bromophenol blue (λ max = 590 nm) was observed when Mo SA‐N/C was added to the mixture of H 2 O 2 , Br − and phenol red under dark (Figure S7, Supporting Information). Furthermore, no color change was observed when Br − or H 2 O 2 was absent.…”

Section: Resultsmentioning

confidence: 99%

Photothermal‐Amplified Single Atom Nanozyme for Biofouling Control in Seawater

Wang

Luo

et al. 2022

Adv Funct Materials

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Biofouling is a common and expensive problem in medical, food, and maritime industries. Artificial nanozymes as functional mimics of haloperoxidases that boost the formation of cytotoxic hypohalous acids from halides and H2O2 are showing increasing potential as a novel class of ecofriendly antibiofouling materials to combat biofilm formation. A photothermal nanozyme (Mo SA‐N/C) with Mo single atoms as active sites that exhibits haloperoxidase‐mimicking capacity is herein developed. Density functional theory calculations indicate that hydroxyl radical from H2O2 dissociation is the key intermediate for hypobromous acid formation. Upon photoirradiation, Mo SA‐N/C generates heat and accelerates the reaction kinetics substantially. Finally, it is demonstrated that Mo SA‐N/C exerts superior broad‐spectrum antibacterial activity and can be applied as an effective coating additive for inhibiting biofouling in real marine conditions. Taken together, this study opens an avenue for developing biocompatible and photo‐response artificial enzymes for our fight against marine biofouling.

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“…The binding energies at 881.6, 888.6, 897.9, 900.2, 907.1, and 915.7 eV correspond to Ce 4+ while four peaks at 880.2, 884.6, 899.7, and 903.2 eV were attributed to Ce 3+ . [ 27,42 ] The relative amount of Ce 3+ /Ce 4+ for CeO 2 @ZrO 2 was about 64.6%, 1.5 times higher than that for pristine CeO 2 , indicating that cluster structure induced the formation of abundant Ce 3+ defects. Electron paramagnetic resonance (EPR) analysis exhibited the adsorption peak with the g‐factor value located at 2.004 (Figure 2f).…”

Section: Resultsmentioning

confidence: 99%

“…With the unique hybrid cluster structure, the haloperoxidase‐mimicking activity of CeO 2 @ZrO 2 in selective bromination oxidation of Br − were evaluated using phenol red bromination assay. [ 27 ] Typically, phenol red indicator (λ max = 430 nm) could be selectively brominated by vanadium‐based haloperoxidases to its fourfold oxidative bromination product bromophenol blue (λ max = 590 nm) in the presence of H 2 O 2 and Br − , which can be used as a standard substrate of haloperoxidase‐like catalytic reaction. [ 44 ] Such conversion led to an obvious color change from yellow to blue and thus can be monitored spectrophotometrically.…”

Section: Resultsmentioning

confidence: 99%

Stabilizing Ultrasmall Ceria‐Cluster Nanozyme for Antibacterial and Antibiofouling Applications

Luo

Huo

et al. 2022

Small

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haloperoxidases. [15,16] This kind of natural enzymes can catalyze the two-electron oxidation of halides to microbicidal hypohalous acids (HOX, X: Cl − , Br − , I − ) or analogous oxidized halide species in the presence of hydrogen peroxide (H 2 O 2 ). [17][18][19] Such natural biofilm inhibition utilizing naturally occurring reagents (halide and H 2 O 2 ) represents a promising and environmentally friendly antibiofilm strategy. Nevertheless, natural enzymes often suffer from intrinsic drawbacks such as highcost, poor operational stability, and recyclability. Artificial nanozymes, one kind of nanomaterials combining nanoscale and enzyme-like catalytic functionalities, exhibit advantages such as low-cost and high durability. [20][21][22][23][24] Interestingly, some nanomaterials (e.g., vanadium pentoxide and ceria) have been explored as haloperoxidase-mimicking nanozymes. [25][26][27][28][29] Although high catalytic activity, the carcinogenicity and mutagenicity of vanadium pentoxide could hinder their large-scale application in marine environment. As a heterogeneous metal oxide nanozyme, mixed-valency nanoceria exhibited significantly enhanced catalytic activity towards haloperoxidase-like reaction in contrast to bulk ceria, [28] highlighting that high surface-to-volume ratio and surface geometric effect could strongly affect the activity of a nanozyme. Nevertheless, the haloperoxidase-like performance of nanoceria is relatively low. From a structural perspective, downsizing ceria to nanocluster scale is of significance for maximizing active component utilization and achieving better haloperoxidase-mimicking performance. Unfortunately, most nanomaterials have large particles owing to the natural tendency of agglomeration.Nanostructured materials involving highly dispersed subnanocluster species on supports have been shown to be crucial for enabling heterogeneous catalysts with high intrinsic activity and unexpected selectivity. [30][31][32][33] Nevertheless, stabilizing goaloriented high-density ultrasmall nanoclusters on solid substrates with uniform size and dispersion has been challenged by the thermodynamic instability of nanocluster, poor interfacial hybrid interaction, as well as chemical synthesis. [34][35][36] Herein we propose a fabrication strategy to fabricate hybrid CeO 2 @ ZrO 2 where high-density ultrasmall ceria clusters (≈0.8 nm) are stabilized on zirconia substrates. This unique feature of heterografting CeO 2 @ZrO 2 nanozyme enabled superior and stable haloperoxidase-mimicking performance in selectively catalyzing the oxidation of bromide with H 2 O 2 to hypobromousThe generation of undesired biofouling in medical and engineering applications results in a reduction in function and durability. Copying functionalities of natural enzymes to combat biofouling by artificial nanomaterials is highly attractive but still challenged by the inferior catalytic activity and specificity principally because of low densities of active sites. Here, an innovate strategy is demonstrated to stabilize high-density ...

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Room temperature synthesis of defective cerium oxide for efficient marine anti-biofouling

Cited by 10 publications

References 46 publications

Antifouling coatings can reduce algal growth while preserving coral settlement

Antifouling coatings can reduce algal growth while preserving coral settlement

Photothermal‐Amplified Single Atom Nanozyme for Biofouling Control in Seawater

Stabilizing Ultrasmall Ceria‐Cluster Nanozyme for Antibacterial and Antibiofouling Applications

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