Insights into Ionic Transport and Structural Changes in Magnetite during Multiple‐Electron Transfer Reactions

Metal oxides, such as Fe₃O₄, hold promise for future battery applications due to their abundance, low cost, and opportunity for high lithium storage capacity. In order to better understand the mechanisms of multiple‐electron transfer reactions leading to high capacity in Fe₃O₄, a comprehensive investigation on local ionic transport and ordering is made by probing site occupancies of anions (O^2?) and cations (Li⁺, Fe³⁺/Fe²⁺) using multiple synchrotron X‐ray and electron‐beam techniques, in combination with ab‐initio calculations. Results from this study provide the first experimental evidence that the cubic‐close‐packed (ccp) O‐anion array in Fe₃O₄ is sustained throughout the lithiation and delithiation processes, thereby enabling multiple lithium intercalation and conversion reactions. Cation displacement/reordering occurs within the ccp O‐anion framework, which leads to a series of phase transformations, starting from the inverse spinel phase and turning into intermediate rock‐salt‐like phases (Li_xFe₃O₄; 0 < x < 2), then into a cation‐segregated phase (Li₂O?FeO), and finally converting into metallic Fe and Li₂O. Subsequent delithiation and lithiation processes involve interconversion between metallic Fe and FeO‐like phases. These results may offer new insights into the structure‐determined ionic transport and electrochemical reactions in metal oxides, and those of other compounds sharing a ccp anion framework, reminiscent of magnetite.     

The role of biomineralization in microbiologically influenced corrosion

Synthetic iron oxides (goethite, -FeO·OH; hematite, Fe₂O₃; and ferrihydrite, Fe(OH)₃) were used as model compounds to simulate the mineralogy of surface films on carbon steel. Dissolution of these oxides exposed to pure cultures of the metal-reducing bacterium, Shewanella putrefaciens, was followed by direct atomic absorption spectroscopy measurement of ferrous iron coupled with microscopic analyses using confocal laser scanning and environmental scanning electron microscopies. During an 8-day exposure the organism colonized mineral surfaces and reduced solid ferric oxides to soluble ferrous ions. Elemental composition, as monitored by energy dispersive x-ray spectroscopy, indicated mineral replacement reactions with both ferrihydrite and goethite as iron reduction occurred. When carbon steel electrodes were exposed to S. putrefaciens, microbiologically influenced corrosion was demonstrated electrochemically and microscopically.     

Biosynthesis of au nanoparticles by a marine bacterium and enhancing their catalytic activity through metal ions and metal oxides

The authors report that a marine Shewanella sp. CNZ-1 is capable of producing Au NPs under various conditions. Results showed that initial concentration of Au(III), pH values and electron donors affected nucleation of Au NPs by CNZ-1, resulting in different apparent color of the as-obtained bio-Au NPs, which were further characterized by UV-Vis, TEM, XRD, and XPS analyses. Mechanism studies revealed that Au(III) was first reduced to Au(I) and eventually reduced to EPS-coated Au⁰ NPs. FTIR and FEEM analyses revealed that some amides and humic acid-like matters were involved in the production of bio-Au NPs through CNZ-1 cells. In addition, the authors also found that the catalytic activity of bio-Au NPs for 4-nitrophenol (4-NP) reduction could be enhanced by various metal ions (Ca²⁺, Cu²⁺, Co²⁺, Fe²⁺, Fe³⁺, Ni²⁺, Sr²⁺, and Cr³⁺) and metal oxides (Fe₃O₄, Al₂O₃, and SiO₂), which is beneficial for their further practical application. The maximum zero-order rate constant k ₁ and first-order rate constant k₂ of all metal ions/oxides supplemented systems can reach 99.65 mg/(L^.min) and 2.419 min⁻¹, which are 11.3- and 12.6-fold higher than that of control systems, respectively. © 2018 American Institute of Chemical Engineers Biotechnol. Prog., 35: e2727, 2019.     

The Prospects of Metal Oxide Nanoradiosensitizers: The Effect of the Elemental Composition of Particles and Characteristics of Radiation Sources on Enhancement of the Adsorbed Dose

Nanoparticles with a high atomic number are of interest as radiosensitizers for radiation therapy of cancer. A variety of nanoparticles and radiation sources makes the challenge of selecting their optimal combinations to achieve maximum irradiation efficacy relevant. In this work, we calculated the values of the dose enhancement factors of elemental compositions of metal oxide nanoparticles (Al₂O₃, TiO₂, MnO₂, Fe₂O₃ and Fe₃O₄, NiO, GeO₂, ZrO₂, CeO₂, Gd₂O₃, Tm₂O₃, HfO₂, Ta₂O₅, and Bi₂O₃), as well as GeO₂ and HfO₂ doped with the rare-earth elements lanthanum or ytterbium in combination with monochromatic photons (1–500 keV) and X-ray radiation corresponding to the radiation of kilovoltage X-ray therapy machines. At a nanoparticle concentration of 10 mg/mL, the maximum values of the dose enhancement factors were from 1.03 to 2.55 for monochromatic radiation and from 1.01 to 2.33 for the studied X-ray spectra. Doping GeO₂ with 20% lanthanum or ytterbium led to an increase in the maximum value of dose enhancement factors by ~10%. Doping HfO₂ did not lead to significant changes in the value of dose-enhancement factors. Thus, all studied elemental compositions of nanoparticles, with the exception of Al₂O₃ (a dose enhancement factor ~1.02), are promising for application in kilovoltage X-ray radiotherapy. At the same time, the complex dependence of dose enhancement factors on the spectral composition of X-ray radiation requires detailed studies of the impact of irradiation conditions on the magnitude of the radiomodifying effect of nanoparticles.

     

Fundamental Understanding and Material Challenges in Rechargeable Nonaqueous Li–O2 Batteries: Recent Progress and Perspective

Energy storage challenges have triggered growing interest in various battery technologies and electrocatalysis. As a particularly promising variety, the Li–O₂ battery with an extremely high energy density is of great significance, offering tremendous opportunities to improve cell performance via understanding catalytic mechanisms and the exploration of new materials. Furthermore, focus on nonaqueous electrolyte‐based Li–O₂ batteries has markedly intensified since there could be a higher probability of commercialization, compared to that of solid‐state or aqueous electrolytes. The recent advancements of the nonaqueous Li–O₂ battery in terms of fundamental understanding and material challenges, including electrolyte stability, water effect, and noncarbon cathode materials are summarized in this review. Further, the current status of water impact on discharge products, possible mechanisms, and parasitic reactions in nonaqueous electrolytes are reviewed for the first time. The key challenges of noncarbon oxygen electrode materials, such as noble metals and metal oxides‐based cathodes, transition metals, transition metal compounds (carbides, oxides) based cathodes as well as noncarbon supported catalysts are discussed. This review concludes with a perspective on future research directions for nonaqueous Li–O₂ batteries.     

Anaerobic Microbial Dissolution of Transition and Heavy Metal Oxides

Anaerobic microbial dissolution of several crystalline, water-insoluble forms of metal oxides commonly associated with the waste from energy production was investigated. An anaerobic N-fixing Clostridium sp. with an acetic, butyric, and lactic acid fermentation pattern, isolated from coal-cleaning waste, solubilized Fe₂O₃ and MnO₂ by direct enzymatic reduction; CdO, CuO, PbO, and ZnO were solubilized by indirect action due to the production of metabolites and the lowering of the pH of the growth medium. Extracellular heat-labile components of the cell-free spent medium obtained from cultures without oxide solubilized a significant amount of Fe₂O₃ (1.7 μmol); however, direct contact with the bacterial cells resulted in the complete dissolution (4.8 μmol) of the oxide. Under identical conditions, the cell-free spent medium solubilized only a small amount of MnO₂ (0.07 μmol), whereas 2.3 μmol of the oxide was solubilized by direct bacterial contact. Reduction of Fe₂O₃ and MnO₂ by Clostridium sp. proceeds at different rates and, possibly, by different enzymatic systems. Fe(III) and Mn(IV) oxides appear to be used as sinks for excess electrons generated from glucose fermentation, since there is no apparent increase in growth of the bacterium concomitant with the reduction of the oxides. Dialysis bag experiments with Co₂O₃ indicate that there is a slight dissolution of Co (0.16 μmol) followed by precipitation or biosorption. Although Mn₂O₃, Ni₂O₃, and PbO₂ may undergo reductive dissolution from a higher to a lower oxidation state, dissolution by direct or indirect action was not observed. Also, Cr₂O₃ and NiO were not solubilized by direct or indirect action. Significant amounts of solubilized Cd, Cu, and Pb were immobilized by the bacterial biomass, and the addition of Cu²⁺ inhibited the growth of the bacterium.     

Cytotoxicity,permeability, and inflammation of metal oxide nanoparticles in human cardiac microvascular endothelial cells

Wide applications and extreme potential of metal oxide nanoparticles (NPs) increase occupational and public exposure and may yield extraordinary hazards for human health. Exposure to NPs has a risk for dysfunction of the vascular endothelial cells. The objective of this study was to assess the cytotoxicity of six metal oxide NPs to human cardiac microvascular endothelial cells (HCMECs) in vitro. Metal oxide NPs used in this study included zinc oxide (ZnO), iron(III) oxide (Fe₂O₃), iron(II,III) oxide (Fe₃O₄), magnesium oxide (MgO), aluminum oxide (Al₂O₃), and copper(II) oxide (CuO). The cell viability, membrane leakage of lactate dehydrogenase, intracellular reactive oxygen species, permeability of plasma membrane, and expression of inflammatory markers vascular cell adhesion molecule-1, intercellular adhesion molecule-1, macrophage cationic peptide-1, and interleukin-8 in HCMECs were assessed under controlled and exposed conditions (12–24 h and 0.001–100 μg/ml of exposure). The results indicated that Fe₂O₃, Fe₃O₄, and Al₂O₃ NPs did not have significant effects on cytotoxicity, permeability, and inflammation response in HCMECs at any of the concentrations tested. ZnO, CuO, and MgO NPs produced the cytotoxicity at the concentration-dependent and time-dependent manner, and elicited the permeability and inflammation response in HCMECs. These results demonstrated that cytotoxicity, permeability, and inflammation in vascular endothelial cells following exposure to metal oxide nanoparticles depended on particle composition, concentration, and exposure time.     

Toxic effects of nanoparticles on bioluminescence activity,seed germination,and gene mutation

The potential environmental toxicities of several metal oxide nanoparticles (NPs; CuO, TiO₂, NiO, Fe₂O₃, ZnO, and Co₃O₄) were evaluated in the context of bioluminescence activity, seed germination, and bacterial gene mutation. The bioassays exhibited different sensitivities, i.e., each kind of NP exhibited a different level of toxicity in each of the bioassays. However, with a few exceptions, CuO and ZnO NPs had most toxic for germination of Lactuca seed (EC₅₀ 0.46 mg CuO/l) and bioluminescence (EC₅₀ 1.05 mg ZnO/l). Three NPs (Co₃O₄, TiO₂, and Fe₂O₃) among all tested concentrations (max. 1,000 mg/l) showed no inhibitory effects on the tested organisms, except for Co₃O₄ NPs on bioluminescence activity (EC₅₀ 62.04 mg/l). The sensitivity of Lactuca seeds was greater than that of Raphanus seeds (EC₅₀ 0.46 mg CuO/l versus 26.84 mg CuO /l ). The ranking of metal toxicity levels on bioluminescence was in the order of ZnO?>?CuO?>?Co₃O₄?>?NiO?>?Fe₂O₃, TiO₂, while CuO?>?ZnO?>?NiO?>?Co₃O₄, Fe₂O₃, TiO₂ on germination. No revertant mutagenic ratio (greater than 2.0) of Salmonella typhimurium TA 98 was observed under any tested condition. These findings demonstrate that several bioassays, as opposed to any single one, are needed for the accurate assessment of NP toxicity on ecosystems.     

Effect of Phosphate on the Corrosion of Carbon Steel and on the Composition of Corrosion Products in Two-Stage Continuous Cultures of Desulfovibrio desulfuricans

A field isolate of Desulfovibrio desulfuricans was grown in defined medium in a two-stage continuous culture apparatus with different concentrations of phosphate in the feed medium. The first state (V1) was operated as a conventional chemostat (D = 0.045 h⁻¹) that was limited in energy source (lactate) or phosphate. The second stage (V2) received effluent from V1 but no additional nutrients, and contained a healthy population of transiently starved or resting cells. An increase in the concentration of phosphate in the medium fed to V1 resulted in increased corrosion rates of carbon steel in both V1 and V2. Despite the more rapid corrosion observed in growing cultures relative to that in resting cultures, corrosion products that were isolated under strictly anaerobic conditions from the two culture modes had similar bulk compositions which varied with the phosphate content of the medium. Crystalline mackinawite (Fe₉S₈), vivianite [Fe₃(PO₄)₂ · 8H₂O], and goethite [FeO(OH)] were detected in amounts which varied with the culture conditions. Chemical analyses indicated that the S in the corrosion product was almost exclusively in the form of sulfides, while the P was present both as phosphate and as unidentified components, possibly reduced P species. Some differential localization of S and P was observed in intact corrosion products. Cells from lactate-limited, but not from phosphate-limited, cultures contained intracellular granules that were enriched in P and Fe. The results are discussed in terms of several proposed mechanisms of microbiologically influenced corrosion.     

Cytotoxicity in the age of nano: The role of fourth period transition metal oxide nanoparticle physicochemical properties

A clear understanding of physicochemical factors governing nanoparticle toxicity is still in its infancy. We used a systematic approach to delineate physicochemical properties of nanoparticles that govern cytotoxicity. The cytotoxicity of fourth period metal oxide nanoparticles (NPs): TiO₂, Cr₂O₃, Mn₂O₃, Fe₂O₃, NiO, CuO, and ZnO increases with the atomic number of the transition metal oxide. This trend was not cell-type specific, as observed in non-transformed human lung cells (BEAS-2B) and human bronchoalveolar carcinoma-derived cells (A549). Addition of NPs to the cell culture medium did not significantly alter pH. Physiochemical properties were assessed to discover the determinants of cytotoxicity: (1) point-of-zero charge (PZC) (i.e., isoelectric point) described the surface charge of NPs in cytosolic and lysosomal compartments; (2) relative number of available binding sites on the NP surface quantified by X-ray photoelectron spectroscopy was used to estimate the probability of biomolecular interactions on the particle surface; (3) band-gap energy measurements to predict electron abstraction from NPs which might lead to oxidative stress and subsequent cell death; and (4) ion dissolution. Our results indicate that cytotoxicity is a function of particle surface charge, the relative number of available surface binding sites, and metal ion dissolution from NPs. These findings provide a physicochemical basis for both risk assessment and the design of safer nanomaterials.     

Assessing the Impact of Iron-based Nanoparticles on pH,Dissolved Organic Carbon,and Nutrient Availability in Soils

With the ongoing commercialization of nanotechnology products, the increasing use of engineered nanoparticles (NPs) could lead potentially to environmental risks. This study investigated the dynamic influences of three iron-based NPs (Fe⁰, Fe₃O₄, and Fe₂O₃) applied into a red soil (RS) and a Wushan soil (WS) with different application rates (2 to 6 g kg^?1) on soil physicochemical properties such as pH, dissolved organic carbon (DOC), available ammonium nitrogen (NH₄ ⁺-N), available phosphorus (AP), and enzymatic activities. The results showed that the addition of Fe⁰ NPs increased DOC and available NH₄ ⁺-N, but significantly decreased AP, while Fe₃O₄ and Fe₂O₃ NPs slightly reduced soil pH in both soils and significantly declined available NH₄ ⁺-N in the WS and AP in the RS. No significant difference was observed between the effects of Fe₃O₄ and Fe₂O₃ NPs on soil properties except AP in the RS. All iron-based NPs decreased the activities of urease and acid phosphatase in both soils. The effects on soil physicochemical properties, especially available NH₄ ⁺-N and AP induced by iron-based NPs, varied greatly with soil types. These results implied that cautions should be paid for the environmental application of iron-based NPs, especially iron oxide NPs in soils.     

Improved degradation of lignocellulosic biomass pretreated by Fenton-like reaction using Fe<Subscript>3</Subscript>O<Subscript>4</Subscript> magnetic nanoparticles

The ability of Fe₃O₄ Fenton-like reaction to produce glucose from lignocellulosic biomass was investigated. Fe₃O₄ magnetite nanoparticles were chemically synthesized from iron salts (a mixture of 1 M FeCl₂ and 2M FeCl₃) using an ammonia solution (30% NH₄OH). The synthesized Fe₃O₄ nanoparticles were further characterized by X-ray photoelectron spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy, and transmission electron microscopy. Reed stems and rice straw biomasses pretreated with optimized Fenton-like reagents (Fe₃O₄ and H₂O₂) increased glucose production by 177 and 87%, respectively, compared to the control without the catalysts.     

Fabrication of Nano-engineered Transparent Conducting Oxides by Pulsed Laser Deposition

Nanosecond Pulsed Laser Deposition (PLD) in the presence of a background gas allows the deposition of metal oxides with tunable morphology, structure, density and stoichiometry by a proper control of the plasma plume expansion dynamics. Such versatility can be exploited to produce nanostructured films from compact and dense to nanoporous characterized by a hierarchical assembly of nano-sized clusters. In particular we describe the detailed methodology to fabricate two types of Al-doped ZnO (AZO) films as transparent electrodes in photovoltaic devices: 1) at low O₂ pressure, compact films with electrical conductivity and optical transparency close to the state of the art transparent conducting oxides (TCO) can be deposited at room temperature, to be compatible with thermally sensitive materials such as polymers used in organic photovoltaics (OPVs); 2) highly light scattering hierarchical structures resembling a forest of nano-trees are produced at higher pressures. Such structures show high Haze factor (>80%) and may be exploited to enhance the light trapping capability. The method here described for AZO films can be applied to other metal oxides relevant for technological applications such as TiO₂, Al₂O₃, WO₃ and Ag₄O₄.     

A possible theranostic approach of chitosan-coated iron oxide nanoparticles against human colorectal carcinoma (HCT-116) cell line

Iron oxides have become increasingly popular for their use as a diagnostic and therapeutic tool in oncology. This study aimed to improve pharmacological valuable of Fe₃O₄, which may be use to diagnosis colorectal cancers (CRC). Here, we have developed chitosan (CS) coated Fe₃O₄ through a cost-effective procedure. First, we determined the characterization of OA-C-Fe₃O₄ by FTIR, UV–Vis spectra, and TEM. Then, we evaluated the photodynamic therapeutic (PDT) activity of OA-C-Fe₃O₄ in human colorectal carcinoma cell lines (HCT 116). Current results revealed that the light-induced enhanced reactive oxygen species (ROS) activity of the nanoparticles (NPs) and caused cell death via the activity of caspase 9/3. The in vitro magnetic resonance imaging (MRI) experiments in (HCT 116) and human embryonic kidney cells (HEK 293) illustrated that nanohybrid is an effective MRI contrasting agents for the diagnosis of colorectal cancer.     

Biogeochemical Properties of Bacteriogenic Iron Oxides

Bacteriogenic iron oxides (BIOS) are composite materials that consist of intact and partly degraded remains of bacterial cells intermixed with variable amounts of poorly ordered hydrous ferric oxide (HFO) minerals. They form in response to chemical or bacterial oxidation of Fe²⁺, which gives rise to Fe³⁺. Once formed, Fe³⁺ tends to undergo hydrolysis to precipitate in association with bacterial cells. In acidic systems where the chemical oxidation of Fe²⁺ is slow, bacteria are capable of accelerating the reaction by several orders of magnitude. At circumneutral pH, the chemical oxidation of Fe²⁺ is fast. This requires Fe²⁺ oxidizing bacteria to exploit steep redox gradients where low pO₂ slows the abiotic reaction enough to allow the bacteria to compete kinetically. Because of their reactive surface properties, BIOS behave as potent sorbents of dissolved metal ions. Strong enrichments of Al, Cu, Cr, Mn, Sr, and Zn in the solid versus aqueous phase (log 10 K_d values range from 1.9 to 4.2) are common; however, the metal sorption properties of BIOS are not additive owing to surface chemical interactions between the constituent HFO and bacteria. These interactions have been investigated using acid-base tritrations, which show that the concentration of high pK_a sites is reduced in BIOS compared to HFO. At the same time, hydroxylamine insoluble material (i.e., residual bacterial fraction) is enriched in low pK_a sites relative to both BIOS and HFO. These differences indicate that low pK_a or acidic sites associated with bacteria in BIOS interact specifically with high pK_a or basic sites on intermixed HFO.     

Correlation of proton release and ultraviolet difference spectra associated with metal binding by transferrin

A variety of metal ions can bind to the iron-transport protein, transferrin, at two specific sites. For each metal ion, a carboxylate anion is concomitantly bound. Six metal ions which were examined fall into two classes based on proton release and ultraviolet spectral changes which accompany binding to the protein. Class II ions, which include Cu²⁺ and Zn²⁺, release approximately 2 H⁺/metal bond. Class III ions, which include Fe³⁺, Ga³⁺, Al³⁺, and VO²⁺, release approximately 3 H⁺/metal bound. The increase in absorbance near 242 nm, characteristic of tyrosine ionization, has the ratio 0.55–0.75 for class II:class III ions. Both Fe³⁺ and Cu²⁺ form metal-transferrin-oxalate complexes in the presence of excess C₂O₄^2?. Fe³⁺ releases close to 3 H⁺/metal whether forming oxalate or bicarbonate complexes with transferrin. Binding of Cu²⁺ to transferrin releases 2 H⁺/metal in the presence of C₂O^2?₄ or HCO₃^?. Since equal numbers of H⁺/metal are released for both anions, it is likely that the bicarbonate ion does not lose its proton, and remains as HCO₃^? in transferrin. These results are interpreted in terms of possible combinations of ligands at the metal binding sites.     

Inorganic nitric oxide metabolites participating in no-dependent modifications of biopolymers

Biogenous nitric(II) oxide (NO), the higher nitrogen oxides (NO₂, isomeric N₂O₃ and N₂O₄) that are NO-derived in vivo, and the products of their transformations are active compounds capable of reactions with biopolymers and low-molecular metabolites. These reactions are often considered to be various NO-dependent modifications (NODMs). Nitration, nitrosylation, nitrosation, and other NODMs play key roles in the regulation of the most important biochemical processes. In this review, we briefly discuss the metabolic reactions of nitrogen oxides that supply active intermediates for NODMs, the NODM reaction products, and some mechanisms of NODM reparation that allow the recovery of chemically intact biopolymer molecule from a NODM modified (chemically damaged) form. For example, residues of 3-nitrotyrosine arising due to the NODM reactions of proteins can be reduced to unsubstituted Tyr residues as a result of alternative NODM reactions through intermediate diazotyrosine derivatives. The heterogeneity of a medium in vivo is an important factor controlling the proceeding of NODM reactions. We showed that many processes determining NODM efficiency proceed differently in the heterogeneous media of organisms and in homogeneous aqueous solutions.     

Oil field microorganisms cause highly localized corrosion on chemically inhibited carbon steel

Carbon steel pipelines, a means for crude oil transportation, occasionally experience highly localized perforation caused by microorganisms. While microorganisms grown in laboratory culture tend to corrode steel specimens unevenly, they rarely inflict a corrosion morphology consistent with that of pipelines, where centimetre-sized corrosion features are randomly distributed within vast stretches of otherwise pristine metal surface. In this study, we observed that corrosion inhibitors (CIs), widely used for the control of acid gas (H₂S, CO₂) corrosion in oil fields, also affect microbial growth and activity. Inhibited carbon steel resisted biofilm formation and underwent negligible corrosion (< 0.002 mm Fe⁰ year⁻¹), despite 15 months of exposure to oil field waters harbouring a diverse microbiome. In contrast, physical scavenging of CI in these waters led to severe and highly localized corrosion (up to 0.93 mm Fe⁰ year⁻¹) underneath biofilms dominated by methanogenic archaea and sulfate-reducing bacteria. A sharp decline in CI concentration, as well as its active components, quaternary ammonium compounds (QACs), correlated with microbial sulfidogenesis. CIs are ubiquitously present in oil field waters and play an underappreciated role in microbial corrosion mitigation. Physical and biological scavenging of CIs may create local differences in steel inhibition effectiveness and thus result in highly localized corrosion.     

Retarded Charge–Carrier Recombination in Photoelectrochemical Cells from Plasmon‐Induced Resonance Energy Transfer

N‐type metal oxides such as hematite (α‐Fe₂O₃) and bismuth vanadate (BiVO₄) are promising candidate materials for efficient photoelectrochemical water splitting; however, their short minority carrier diffusion length and restricted carrier lifetime result in undesired rapid charge recombination. Herein, a 2D arranged globular Au nanosphere (NS) monolayer array with a highly ordered hexagonal hole pattern (hereafter, Au array) is introduced onto the surface of photoanodes comprised of metal oxide films via a facile drying and transfer‐printing process. Through plasmon‐induced resonance energy transfer, the Au array provides a strong electromagnetic field in the near‐surface area of the metal oxide film. The near‐field coupling interaction and amplification of the electromagnetic field suppress the charge recombination with long‐lived photogenerated holes and simultaneously enhance the light harvesting and charge transfer efficiencies. Consequently, an over 3.3‐fold higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) is achieved for the Au array/α‐Fe₂O₃. Furthermore, the high versatility of this transfer printing of Au arrays is demonstrated by introducing it on the molybdenum‐doped BiVO₄ film, resulting in 1.5‐fold higher photocurrent density at 1.23 V versus RHE. The tailored metal film design can provide a potential strategy for the versatile application in various light‐mediated energy conversion and optoelectronic devices.