Efficient Photocatalytic H2 O2 Production Ability of a Novel Graphitic Carbon Nitride/Carbon Composites under Visible Light.

In the present work, using one-step calcination of a mixture made of potassium hydroxide (KOH), melamine, and microplastics, this work prepares a novel graphitic carbon nitride/carbon (g-C3 N4 /C) composite, which can be employed to photo-catalytically produce hydrogen peroxide (H2 O2 ) at a high rate up to 6.146 mmol g-1 h-1 under visible light irradiation. By analyzing the energy band structure of the catalyst, the production of H2 O2 in this system consists of two single-electron reactions. The modification of KOH makes abundant N-vacancies caused by cyano-groups in g-C3 N4 , enhancing the electron absorption ability. Moreover, the introduction of graphitic carbon increases its specific surface area and porosity and improves the adsorption ability of O2 . Simultaneously, their synergism reduces the g-C3 N4 band gap, making both the conduction-band and valence-band positions more negative, showing enhanced reduction ability, lowering the energy barrier for oxygen reduction, and greatly improving the photogeneration performance of H2 O2 .

Oxygen Vacancy and Core-Shell Heterojunction Engineering of Anemone-Like CoP@CoOOH Bifunctional Electrocatalyst for Efficient Overall Water Splitting.

Constructing cost-efficient and robust bifunctional electrocatalysts for both neutral and alkaline water splitting is highly desired, but still affords a great challenge, due to sluggish hydrogen/oxygen evolution reaction (HER/OER) kinetics. Herein, an in situ integration engineering strategy of oxygen-vacancy and core-shell heterojunction to fabricate an anemone-like CoP@CoOOH core-shell heterojunction with rich oxygen-vacancies supported on carbon paper (CoP@CoOOH/CP), is described. Benefiting from the synergy of CoP core and oxygen-vacancy-rich CoOOH shell, the as-obtained CoP@CoOOH/CP catalyst displays low overpotentials at 10 mA cm-2 for HER (89.6 mV/81.7 mV) and OER (318 mV/200 mV) in neutral and alkaline media, respectively. Notably, a two-electrode electrolyzer, using CoP@CoOOH/CP as bifunctional catalyst to achieve 10 mA cm-2 , only needs low-cell voltages in neutral (1.65 V) and alkaline (1.52 V) electrolyte. Besides, systematically experimental and theoretical results reveal that the core-shell heterojunction efficiently accelerates the catalytic kinetics and strengthens the structural stability, while rich oxygen-vacancies efficiently decrease the kinetic barrier and activation energy, and reduce the energy barrier of the rate-determining-step for OER intermediates, thus intrinsically boosting OER performance. This work clearly demonstrates that oxygen-vacancy and core-shell heterojunction engineering provide an effective strategy to design highly-efficient non-precious, bi-functional electrocatalysts for pH-universal water splitting.

Ternary Mo2 NiB2 as a Superior Bifunctional Electrocatalyst for Overall Water Splitting.

Transition metal borides are considered as promising electrocatalysts for water splitting due to their metallic conductivity and good durability. However, the currently reported monometallic and noncrystalline multimetallic borides only show generic and monofunctional catalytic activity. In this work, the authors design and successfully synthesize highly crystalline ternary borides, Mo2 NiB2 , via a facile solid-state reaction from pure elemental powders. The as-synthesized Mo2 NiB2 exhibits very low overpotentials for both the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), that is, 280 and 160 mV to reach a current density of 10 mA cm-2 , in alkaline media. These values are much lower from the ones observed over monometallic borides, that is, Ni2 B and MoB, and the lowest among all nonprecious metal borides. By loading Mo2 NiB2 onto Ni foams as both cathode and anode electrode for overall water splitting applications, a low cell voltage of 1.57 V is required to achieve a current density of 10 mA cm-2 , comparable with the value required from the Pt/C||IrO2 /C couple (1.56 V). The proposed synthesis strategy can be used for the preparation of cost-effective, multi-metallic crystalline borides, as multifunctional electrocatalysts.

Understanding the Surface Reconstruction on Ternary Wx CoBx for Water Oxidation and Zinc-Air Battery Applications.

Here, the synthesis of a series of pure phase metal borides is reported, including WB, CoB, WCoB, and W2 CoB2 , and their surface reconstruction is studied under the electrochemical activation in alkaline solution. A cyclic voltammetric activation is found to enhance the activity of the CoB and W2 CoB2 precatalysts due to the transformation of their surfaces into the amorphous CoOOH layer with a thickness of 3-4 nm. However, such surface transformation does not happen on the WB and WCoB due to their superior structure stability under the applied voltage, highlighting the importance of metal components for the surface reconstruction process. It is found that, compared with CoB, the W2 CoB2 surface shows a quicker reconstruction with a larger active surface area due to the selective leaching of the W from its surface. In the meantime, the metallic W2 CoB2 core underneath the CoOOH layer shows a better promotion of its oxygen evolution reaction (OER) performance than CoB. Therefore, the ternary W2 CoB2 shows better OER performance than the CoB, as well as the WB and WCoB. It is also found that the mixture of W2 CoB2 with Pt/C as the catalysts in air electrode for rechargeable Zn-air battery (ZAB), shows better performance than the IrO2 -Pt/C couple-based ZAB.

Cost Effective Synthesis of Graphene Nanomaterials for Non-Enzymatic Electrochemical Sensors for Glucose: A Comprehensive Review.

The high conductivity of graphene material (or its derivatives) and its very large surface area enhance the direct electron transfer, improving non-enzymatic electrochemical sensors sensitivity and its other characteristics. The offered large pores facilitate analyte transport enabling glucose detection even at very low concentration values. In the current review paper we classified the enzymeless graphene-based glucose electrocatalysts' synthesis methods that have been followed into the last few years into four main categories: (i) direct growth of graphene (or oxides) on metallic substrates, (ii) in-situ growth of metallic nanoparticles into graphene (or oxides) matrix, (iii) laser-induced graphene electrodes and (iv) polymer functionalized graphene (or oxides) electrodes. The increment of the specific surface area and the high degree reduction of the electrode internal resistance were recognized as their common targets. Analyzing glucose electrooxidation mechanism over Cu- Co- and Ni-(oxide)/graphene (or derivative) electrocatalysts, we deduced that glucose electrochemical sensing properties, such as sensitivity, detection limit and linear detection limit, totally depend on the route of the mass and charge transport between metal(II)/metal(III); and so both (specific area and internal resistance) should have the optimum values.

Nanostructure Engineering of Metal-Organic Derived Frameworks: Cobalt Phosphide Embedded in Carbon Nanotubes as an Efficient ORR Catalyst.

Heteroatom doping is considered an efficient strategy when tuning the electronic and structural modulation of catalysts to achieve improved performance towards renewable energy applications. Herein, we synthesized a series of carbon-based hierarchical nanostructures through the controlled pyrolysis of Co-MOF (metal organic framework) precursors followed by in situ phosphidation. Two kinds of catalysts were prepared: metal nanoparticles embedded in carbon nanotubes, and metal nanoparticles dispersed on the carbon surface. The results proved that the metal nanoparticles embedded in carbon nanotubes exhibit enhanced ORR electrocatalytic performance, owed to the enriched catalytic sites and the mass transfer facilitating channels provided by the hierarchical porous structure of the carbon nanotubes. Furthermore, the phosphidation of the metal nanoparticles embedded in carbon nanotubes (P-Co-CNTs) increases the surface area and porosity, resulting in faster electron transfer, greater conductivity, and lower charge transfer resistance towards ORR pathways. The P-Co-CNT catalyst shows a half-wave potential of 0.887 V, a Tafel slope of 67 mV dec-1, and robust stability, which are comparatively better than the precious metal catalyst (Pt/C). Conclusively, this study delivers a novel path for designing multiple crystal phases with improved catalytic performance for energy devices.

Built-in electric field in NiO-CuO heterostructures to regulate the hydroxide adsorption sites for 5-hydroxymethylfurfural electrooxidation assisted hydrogen production.

The development of catalysts with suitable adsorption behavior for the reaction molecules and the elucidation of their internal structure-adsorption-catalytic activity relationships are crucial for the electrooxidation of 5-hydroxymethylfurfural (HMF). In this work, NiO-CuO heterostructures with a spontaneous built-in electric field (BEF) are specifically designed and used to regulate the OH- adsorption site for freeing up the active site of HMF for the HMF oxidation reaction (HMFOR). The mechanism driving electron pumping/accumulation of the BEF is examined by X-ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS). Electrochemical data and theoretical calculations show that BEF modulates the adsorption energy and adsorption site of substrate molecules, thereby enhancing the performance of HMFOR and hydrogen evolution reaction (HER). Notably, the NiO-CuO electrode demonstrates high 2,5-Furandicarboxylic acid (FDCA) selectivity (99.76 %) and generation rate (13.79 mmol gcat-1 h-1). It only requires 1.33 V to obtain a current density of 10 mA cm-2 for HMFOR-coupled H2 evolution. This research introduces a novel approach by regulating the adsorption of reactive molecules for HMFOR-assisted H2 evolution.

Agglomeration inhibition engineering of nickel-cobalt alloys by a sacrificial template for efficient urea electrolysis.

Designing efficient non-precious metal-based catalysts for urea oxidation reaction (UOR) is essential for achieving energy-saving hydrogen production and the treatment of wastewater containing ammonia. In this study, sodium dodecyl sulfate (SDS) is employed as a sacrificial template to synthesize NiCo alloy nanowires (NiCo(SDS)/CC), and the instinct formation mechanism is investigated. It is found that SDS can inhibit the Ostwald ripening during hydrothermal and calcination processes, which could release abundant active cobalt, thereby modulating the electronic structure to promote the catalytic reaction. Moreover, SDS as a sacrificial template can induce the deposition of metal atoms and increase the specific surface area of the catalyst, providing abundant active sites to accelerate the reaction kinetics. As expected, the NiCo(SDS)/CC exhibits good activity for both UOR and hydrogen evolution reactions (HER) and it requires only 1.31 V and -86 mV to obtain a current density of ±10 mA cm-2, respectively. This work provides a new strategy for reducing the agglomeration of transition metals to design high-performance composite catalysts for urea oxidation.

Tailoring competitive adsorption sites of hydroxide ion to enhance urea oxidation-assisted hydrogen production.

Alloys with bimetallic electron modulation effect are promising catalysts for the electrooxidation of urea. However, the side reaction oxygen evolution reaction (OER) originating from the competitive adsorption of OH- and urea severely limited the urea oxidation reaction (UOR) activity on the alloy catalysts. This work successfully constructs the defect-rich NiCo alloy with lattice strain (PMo-NiCo/NF) by rapid pyrolysis and co-doping. By taking advantage of the compressive strain, the d-band center of NiCo is shifted downward, inhibiting OH- from adsorbing on the NiCo site and avoiding the detrimental OER. Meanwhile, the oxygenophilic P/Mo tailored specific adsorption sites to adsorb OH- preferentially, which further released the NiCo sites to ensure the enriched adsorption of urea, thus improving the UOR efficiency. As a result, PMo-NiCo/NF only requires 1.27 V and -57 mV to drive a current density of ±10 mA cm-2 for UOR and hydrogen evolution reaction (HER), respectively. With the guidance of this work, reactant competing adsorption sites could be tailored for effective electrocatalytic performance.

Novel and efficient Bi-doped CoTe nano-solar evaporators embedded on leno weave cotton gauze for efficient solar-driven desalination.

Solar-driven desalination is considered an alternative to the conventional desalination due to its nearly zero carbon footprint and ease of operating in remote areas. Water can be purified wherever sunlight is available, providing a viable solution to water shortage. Metal chalcogenide-based materials are revolutionary for solar evaporators due to their excellent photothermal conversion efficiency, facile synthesis methods, stability, and low cost. Herein we present a prototype Bi-doped CoTe nano-solar evaporator embedded on leno weave cotton gauze (Bi/CoTe@CG) using the sonication process. The nano-solar evaporator was synthesized using a simple hydrothermal approach to provide an opportunity to scale up. The as designed solar evaporator consisting of 5 % Bi/CoTe@CG showed an excellent water flux of 2.38 kg m-2 h-1 upon one sun radiation (1 kW m-2), considered among the highest literature-reported values. The introduced solar evaporator showed excellent solar efficiency of 96.7 %, good stability, and reusability for five cycles of one hour. The best doping ratio of Bi in CoTe was obtained as Bi0.5Co9.5Te with a contact angle of 11.9° in powder form. The hydrophilic nature of the designed solar-evaporator increased the water interaction with the embedded nano-solar evaporator, which helps the transfer of the heat to nearby water molecules, break their hydrogen bonding and increase the evaporation rate. The ion concentration, of the desalinated pure water collected using Bi/CoTe@CG, decreased by many orders of magnitude and it is far below the limit of WHO standards for Na+ and K+. Thus, a self-floating Bi-doped CoTe nano-solar evaporator deposited on cotton gauze (CG) is an excellent solar evaporator for seawater desalination. The proposed solar evaporator is another step towards introducing environmentally friendly desalination methods.

Engineering Mn-Doped CdS Thin Films Through Chemical Bath Deposition for High-Performance Photoelectrochemical Water Splitting.

Doping conventional materials with a second element is an exciting strategy for enhancing catalytic performance via electronic structure modifications. Herein, Mn-doped CdS thin films were successfully synthesized with the aid of the chemical bath deposition (CBD) by varying the pH value (8, 10, and 12) and the surfactant amount (20, 40, 60 mg). Different morphologies like nano-cubes, nanoflakes, nano-worms, and nanosheets were obtained under different deposition conditions. The optimized Mn-doped CdS synthesized at pH=8 exhibited better photoelectrochemical (PEC) performance for oxygen evolution reaction (OER) than pure CdS films, with a maximum photocurrent density of 300 µA/cm2 at an external potential of 0.5 V, under sunlight illumination. The observed performance is attributed to the successful Mn doping, porosity, high surface area, and nanosphere morphology.

Efficient photocatalytic hydrogen peroxide production over S-scheme In2S3/molten salt modified C3N5 heterojunction.

Graphitic phase carbon nitride (g-C3N5), as a novel n-type metal-free material, is employed as a visible light-receptive catalyst because of its narrow band gap and abundant nitrogen. To overcome the low carrier mobility efficiency of g-C3N5, its modification by K ions was adopted. In addition, In2S3 was selected to couple with modified g-C3N5 to overcome the recombination of photogenerated e-/h+. As a novel photocatalytic material, it was proven to possess a high visible light absorption capacity and a strong H2O2 production ability (up to 3.89 mmol⋅L-1 in 2 h). Moreover, a S-scheme heterojunction structure was successfully constructed between the two materials, which was tested and confirmed to be successful in raising the photogenerated e-/h+ separation efficiency. Ultimately, the primary processes of photocatalytic H2O2 production were summarized by superoxide radical and rotating disc electron measurements. This research provides a fresh perspective for the synthesis of C3N5-based S-scheme heterojunction photocatalysts for producing H2O2.

Efficient photocatalytic hydrogen evolution: Linkage units engineering in triazine-based conjugated porous polymers.

Conjugated porous polymers (CPPs) have been widely reported as promising photocatalysts. However, the realization of powerful photocatalytic hydrogen production performance still benefits from the rational design of molecular frameworks and the appropriate choice of building monomers. Herein, we synthesized two novel conjugated porous polymers (CPPs) by copolymerizing pyrene and 1,3,5-triazine building blocks. It is found that minor structural changes in the peripheral groups of the triazine units can greatly affect the photocatalytic activity of the polymers. Compared with the phenyl-linkage unit, the thiophene-linkage unit can give CPP a wider absorption range of visible light, a narrower band gap, a higher transmission and separation efficiency of photo-generated carriers (electrons/holes), and a better interface contact with the photocatalytic reaction solution. The catalyst containing thiophene-triazine (ThPy-CPP) has an efficient photocatalytic hydrogen evolution rate of 21.65 and 16.69 mmol g-1h-1 under full-arc spectrum and visible light without the addition of a Pt co-catalyst, respectively, much better than the one containing phenyl-triazine (PhPy-CPP, only 5.73 and 3.48 mmol g-1h-1). This study provides a promising direction to design and construct highly efficient, cost-effective CPP-based photocatalysts, for exploring the application of noble metal-free catalysts in photocatalytic hydrogen evolution.

Two-stage confinement derived small-sized highly ordered L10-PtCoZn for effective oxygen reduction catalysis in PEM fuel cells.

Intermetallic ordered PtCo is effective for high oxygen reduction reaction (ORR) activity and stability. However, preparing small-sized, highly ordered PtM alloys is still challenging. Herein, we report a controlled two-stage confinement strategy, in which highly ordered PtCoZn/NC nanoparticles of 5.3 nm size were prepared in a scalable process. The contradiction between the high ordering degree with the small particle size as well as the atomic migration with the space confinement was well resolved. An outstanding PEMFC performance was achieved for L10-PtCoZn/NC with a high mass activity (MA) of 1.21 A/mgPt at 0.9 ViR-free, 80.1 % MA retention after 30 k cycles in H2-O2 operation, and a high mass-specific power density of 8.24 W mg-1Pt in H2-Air operation with a slight loss of cell voltage@0.8 A cm-2 of 28 mV after 30 k cycles. The high performance can be ascribed to the high Pt area exposure, the enhanced Pt-Co coupling, and the prevented agglomeration in the mesoporous carbon wall. Overall, this strategy may contribute to the commercialization of fuel cells.

Enhanced photocatalytic hydrogen evolution activity of co-catalyst free S-scheme polymer heterojunctions via ultrasonic assisted reorganization in solvent.

In this work, two donor-acceptor linear conjugated polymers were designed and synthesized based on thianthrene-5,5,10,10-tetraoxide (TTO) as the acceptor unit, benzo[1,2-b:4,5-b']dithiophene derivative (Py1) and thiophene (Py2) as the donor units, respectively. The Py1/Py2 composite was prepared by physical ball milling of the two polymers in a mixture, which was further treated with a N-methyl-2-pyrrolidone (NMP)-assisted sonication treatment, and the obtained catalyst was named N-Py1/Py2. Compared with the single polymer or Py1/Py2, the FTIR characteristic peaks of O=S=O have a red shift for N-Py1/Py2, accompanied by a profound change in morphology. Furthermore, N-Py1/Py2 has a broader light response and more efficient separation and transport of charge carriers, and as a result it exhibits a higher photocatalytic hydrogen evolution rate (26.5 mmol g-1 h-1) without the involvement of any co-catalyst than Py1/Py2 catalyst (3.56 mmol g-1 h-1). The underlying mechanism for the enhanced photocatalytic activity by the sonication treatment in NMP is discussed based both on experimental and theoretical calculation data.

Recent Advances in Transition Metal Tellurides (TMTs) and Phosphides (TMPs) for Hydrogen Evolution Electrocatalysis.

The hydrogen evolution reaction (HER) is a developing and promising technology to deliver clean energy using renewable sources. Presently, electrocatalytic water (H2O) splitting is one of the low-cost, affordable, and reliable industrial-scale effective hydrogen (H2) production methods. Nevertheless, the most active platinum (Pt) metal-based catalysts for the HER are subject to high cost and substandard stability. Therefore, a highly efficient, low-cost, and stable HER electrocatalyst is urgently desired to substitute Pt-based catalysts. Due to their low cost, outstanding stability, low overpotential, strong electronic interactions, excellent conductivity, more active sites, and abundance, transition metal tellurides (TMTs) and transition metal phosphides (TMPs) have emerged as promising electrocatalysts. This brief review focuses on the progress made over the past decade in the use of TMTs and TMPs for efficient green hydrogen production. Combining experimental and theoretical results, a detailed summary of their development is described. This review article aspires to provide the state-of-the-art guidelines and strategies for the design and development of new highly performing electrocatalysts for the upcoming energy conversion and storage electrochemical technologies.

Enhanced oxygen reduction and methanol oxidation reaction over self-assembled Pt-M (M = Co, Ni) nanoflowers.

Herein, we introduce a facile approach to synthesize a unique class of Pt-M (M = Ni, Co) catalysts with a nanoflower structure for boosting both oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). By controlling the surface-active agents, we modified the functional groups surrounding the Pt atoms, tuned the alloying of Pt and the transition metals Ni and Co, and prepared two different kinds of nanodendrites. Their successful synthesis depends on the selection and amount of surfactants (hexadecyltrimethylammonium bromide (CTAB), Polyvinylpyrrolidone (PVP)). Besides, by controlling reaction time, we also explored the forming procedures for Pt-Co globularia nanodendrite (Pt-Co GND) and Pt-Ni petalody nanodendrite (Pt-Ni PND). Our investigation highlights the importance of complex nanoarchitecture, which enables surface and interface modification to achieve excellent catalytic performance in fuel cell electrocatalysis. The characterization of the as-prepared catalysts reveals a high electrochemical surface area and mass activity (2041 mAmgPt-1and 950 mAmgPt-1 for Pt-Co GND and Pt-Ni PND, respectively, for ORR). Furthermore, Pt-Co GND showed a high MOR activity, with a mass activity value recorded at 1615 mAmgPt-1 which is far superior to that for Pt/C. Moreover, both catalysts retain high activity after accelerated durability tests (ADTs). The electron transfer number was calculated by performing the rotating ring-disk electrode (RRDE) measurements. Due to abundant active sites of Pt, both Pt-Co GND and Pt-Ni PND exhibit a 4e- pathway for ORR with electron transfer number of >3.95.

Preparation and characterization of novel Niln2S4/UiO-66 photocatalysts for the efficient degradation of antibiotics in water.

Photocatalysis is considered an economical, environmentally friendly, and effective technology for removing pollutants. The construction of Z-Scheme heterojunctions has been identified as one of the feasible solutions capable of enhancing the photocatalytic activity. Herein, a series of visible light responsive photocatalysts (NiIn2S4/UiO-66 composites) with excellent activity and stability were prepared by using a solvothermal process. It is found that 20 mg L-1 of tetracycline (TC) could be almost completely degraded under visible light irradiation within 1 h, when the mass ratio of NiIn2S4 to UiO-66 is 0.5:1 (NISU-0.5) and the solution pH = 11. In addition, after six cycles, the degradation rate of tetracycline photocatalyzed by NISU-0.5 still reach up to 90%. Ultraviolet photoelectron spectra (UPS), X-ray photoelectron spectra (XPS) and electron spin resonance measurements (ESR) confirm the formation of the Z-Scheme heterostructure between NiIn2S4 and UiO-66. The synergistic effect between built-in electric field, energy band bending and coulomb interactions in interface of Z-Scheme heterojunction is conducive to restrain the recombination of photogenerated electrons and holes, which greatly improve the photocatalytic activity. In conclusion, this study offers a new thought for design and synthesis of Z-Scheme heterojunctions and provides a cost-effective strategy for solving environmental pollution and energy problems in the future.

Highly stable cathodes for proton exchange membrane fuel cells: Novel carbon supported Au@PtNiAu concave octahedral core-shell nanocatalyst.

Despite the remarkable research efforts, the lack of ideal activity and state-of-the-art electrocatalysts remains a substantial challenge for the global application of fuel cell technology. Herein, is reported the synthesis of Au@PtNiAu concave octahedral core-shell nanocatalysts (Au@PtNiAu-COCS) via solvothermal synthesis modification and optimization approach. The special structure generating a large number of step atoms, enhancing the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR) activity and stability. The superior ORR mass activity of the Au@PtNiAu-COCS is 11.22 times than the exhibited of Pt/C initially by Pt loading, and 5.11 times by Pt + Au loading. After 30 k cycles the mass activity remains 78.8% (8.83 times the initial Pt/C activity) and the half-wave potential only shifts 12 mV. Au@PtNiAu-COCS has superior half-cell activity and gives ideal membrane electrode assemblies. Furthermore, for MOR the Au@PtNiAu-COCS show enhanced anti-toxic (tolerant) ability in CO. This work provides a new strategy to develop core-shell structure nanomaterials for electrocatalysis.

Atomic Scale Mechanisms of Multimode Oxide Growth on Nickel-Chromium Alloy: Direct In Situ Observation of the Initial Oxide Nucleation and Growth.

The initial growth mode of oxide on alloy plays a decisive role in the development of protective oxide scales on metals and alloys, which is critical for their functionality for high temperature applications. However, the atomistic mechanisms dictating that the oxide growth remain elusive due to the lack of direct in situ observation of the initial oxide nucleation and growth at atomic-scale. Herein, we employed environmental transmission electron microscopy and the first-principles calculations to elucidate the initial atomic process of nickel-chromium (Ni-Cr) alloy oxidation. We directly revealed three different oxide growth modes of initial NiO islands on Ni-Cr alloy upon oxidation by O2, which result in distinct crystallography and morphology. The multimode oxide growth leads to irregular-shaped oxides, which is shown to be sensitive to the local mass transport. This localization of oxide growth mode is also demonstrated by the identified vigorous competence in oxide growth and thus shown to be kinetically controlled. The concept exemplified here provides insights into the oxide formation and has significant implications in other material and chemical processes involving oxygen gas, such as corrosion, heterogeneous catalysis, and ionic conduction.