Polymer fused GOFe: Light-driven oxygen donor and antiseptics

https://doi.org/10.1016/j.jphotochem.2020.113075Get rights and content

Highlights

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    An all-in-one artificial photosystem PPaba-FeEu@GO is reported.

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    PPaba-FeEu@GO/water system is a reusable light driven O2 generator.

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    An eco-friendly method for the inhibition of bacteria is reported.

Abstract

Phytopathogenic bacteria have been a prominent problem for the growth of plant and agricultural development. Iron-based oxygen generators will be environmental friendly materials for the treatment of phytopathogenic bacteria in hypoxia environment. To develop environmental friendly materials for bacterial treatment, a polymer fused iron(III) nano-complex (PPaba-FeEu@GO) was constructed. The PPaba-FeEu@GO was synthesized by polymerization of 4-aminobenzoic acid Fe(III) complex on the surface of 0.1 % Eu(III)-doped GO. This nano metal complex (PPaba-FeEu@GO) shows enhanced electron mobility and hole diffusion distance, hence it converts water into oxygen under LED light irradiation without adscititious cocatalyst. Moreover, PPaba-FeEu@GO can convert near-infrared light into heat. The photothermal conversion efficiency was calculated as 40.6 %. Therefore, PPaba-FeEu@GO is a light driven oxygen generator and bacterial inhibitor. Our results demonstrate that polymer fused metal-EuGO system will be kinds of reusable materials for bacterial treatment.

Introduction

Phytopathogenic bacteria have been a prominent problem for the growth of plant and agricultural development [1,2]. They induce various bacterial diseases to plant species and influenced grain output. Industrial bactericides have been validated an efficient production for the treatment of phytopathogenic bacteria, which are restricted by their limited biodegradation, large usage, and contamination to environment [[3], [4], [5]]. Nowadays, the protection of plant from bacterial infection has challenged by unceasing bacterial resistance [6,7], sustainable, environment-friendly materials preventing plant from bacterial infection are demanded.

Iron(III) is an abundant source in the earth. Haematite (α-Fe2O3) or amorphous iron oxide materials have been reported as environmentally friendly photocatalysts for water oxidation using RuII complex as co-catalysts, thus produce reactive oxygen species (ROS) with efficient antibacterial capacity [8,9]. It has been demonstrated that α-Fe2O3 nanoparticles could accelerate the kinetics of the water oxidation reaction through the rapid decompose of FeOOH to ·OH and convert to O2 [10]. Previously, we found that polymer united Fe2O3/Ru(II) system can be a stable photocatalyst for water oxidation reaction [11]. However, the water oxidation property of α-Fe2O3 /Ru(II) are limited by dependence of cocatalyst [[12], [13], [14]], and has low electron mobility and small holes diffusion distance, which present a barrier for their catalytic use [15]. In PSII, a close tyrosine residue acts as a charge mediator between catalyst and the light harvester. Li Can et al. reported a partially oxidized graphene as biomimetic tyrosine for charge transfer [16]. To change the lifetime of carriers and the hole migration distance, the thin-layered heterojunction sample of Fe2O3/C–C3N4 and N-doped graphene metal nanocrystals (FeNi@NC) were reported as electrocatalysts for oxygen oxidation [17,18]. It is possible to develop effective photocatalysts with enhanced production rate of ROS for bacterial inhibition by using catalyst doped carbon materials. The carbon-based materials especially graphene (GO) can improve the performance of catalysts due to enhanced charge transfer efficiency [19]. Meanwhile, Eu(III)-MOF or Eu(III) doped nanoparticles can be used to promote water oxidation as Eu3+ has a low reduction potential (The Ered Eu3+/Eu2+ = −0.35 V vs NHE) [20]. We suggest that the conjugated system of Eu(III) ion and graphene will improve the electron transfer, hole migration processes of catalysts, and promote light absorption, resulting in an increase of ROS product. Meanwhile, polymer (such as polydopamine, polyaniline) featured superb biocompatibility and biodegradation [21], can convert light to heat that is triggered by near-infrared (NIR) light as GO [22]. With irradiation of NIR light, heat produced by polymer and GO can inhibit bacterial growth. It is predicted that decoration of GO on polymer united Fe2O3 results in a multifunctional nanocomposite with photo-catalytical and photothermal ability for bacteria killing.

Here, to develop a sustainable, environmentally friendly photocatalysts for water oxidation and antibacterial application, we reported a polymer fused Eu(Ⅲ)-graphene (GO)/Fe2O3 system. It was found that the GO-Eu(Ⅲ) doped Fe2O3 can be LED light driven O2 generator without additional cocatalysts. With irradiation of NIR light, GO-Eu(Ⅲ) doped Fe2O3 showed favorable photothermal sterilization.

Section snippets

Materials and characterization

All reagents were of analytical-reagent grade and were directly used for the following experiments without further purification. 4-Aminobenzoic acid, europium chloride hexahydrate, sodium hydroxide, gadolinium chloride, ferric chloride hydrate, disodium hydrogen phosphate and sodium dihydrogen phosphate were purchased from Sinopharm Chemical Reagent Co. Ltd (Shanghai, China). Graphene oxide was provided by Nanjing XFNANO Materials Technology Co. Ltd (Nanjing, China). Poly (p-aminobenzoic

Characterization of PPaba-FeEu@GO

The PPaba-FeEu@GO was synthesized in one-pot process (Scheme 1). Eu(III) and Fe(III) coordinated with −COOH of 4-aminobenzoic acid doped GO, which can polymerize into poly (p-aminobenzoic acid-aniline) (PPaba) at 160℃ [17]. PPaba-FeEu@GO was a sphere nanoparticle with average size of 350 nm (Fig. 1a). In FT-IR spectra (Fig. 1b), the peak of 1600 cm−1 belonged to vibrational peak of Cdouble bondO bond. The peaks at 565 cm−1 and 476 cm−1 were the characteristic vibration of Fesingle bondO bond, suggesting the

Conclusion

In summary, an artificial mimic photosystem Ⅱ nanoparticle (PPaba-FeEu@GO) had been constructed. With a broad visible light band, PPaba-FeEu@GO could be light driven catalyst for oxygen generator with TOF value of 125 h−1. The nanoparticles showed a well stability in morphology and chemical property and can be recycled. Both the TON and TOF values of PPaba-FeEu@GO were four times than those of previously reported PPaba-Fe/Ru(bpy)3 system. Moreover, well photothermal ability of PPaba-FeEu@GO

Authors' contributions

All authors contributed to the study conception and design.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

CRediT authorship contribution statement

Wei-Yu Mu: Formal analysis, Investigation, Writing - original draft. Wei Wang: Formal analysis, Investigation. Qiu-Yun Chen: Conceptualization, Methodology, Writing - review & editing. Ling-Ling Qu: Writing - review & editing, Supervision.

Acknowledgement

This work was supported by the National Natural Science Foundation of China (grant number 21701056).

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