Important Transition Metal Research Articles

Synthesis of α‐NiS Decorated Fe3S4 Nanohybrid Composite and Its Heterogeneous Fenton Catalysis for Dye Degradation

AbstractGreigite (Fe3S4) and millerite (NiS) are important transition metal sulfides that exhibit light‐driven Fenton catalytic activity. In absence of light, they show limited activity. To utilize these properties without relying on light, we synergized these sulfides to prepare a composite Fe3S4–NiS (FSNS). Under fixed reaction conditions, the composite demonstrated excellent Fenton activity, degrading 93% of fast green dye (FG) and 98.1% of eriochrome black T dye (EBT) within a short reaction time. The mechanism involves electron transfer from the reduced sulfur state (S2−) in both NiS and Fe3S4 to the higher oxidation states of the metal ions viz. Fe3+and Ni3+ to facilitate the redox cyclization in the Fenton process. The catalyst showed high stability for five cyclical tests by recovering it from solution with an external magnet.

Iron: Life’s primeval transition metal

Modern life requires many different metal ions, which enable diverse biochemical functions. It is commonly assumed that metal ions’ environmental availabilities controlled the evolution of early life. We argue that evolution can only explore the chemistry that life encounters, and fortuitous chemical interactions between metal ions and biological compounds can only be selected for if they first occur sufficiently frequently. We calculated maximal transition metal ion concentrations in the ancient ocean, determining that the amounts of biologically important transition metal ions were orders of magnitude lower than ferrous iron. Under such conditions, primitive bioligands would predominantly interact with Fe(II). While interactions with other metals in certain environments may have provided evolutionary opportunities, the biochemical capacities of Fe(II), Fe–S clusters, or the plentiful magnesium and calcium could have satisfied all functions needed by early life. Primitive organisms could have used Fe(II) exclusively for their transition metal ion requirements.

The Theoretical Calculation of the Cu Isotope Fractionation Effect in Solution/Hydrothermal Solution Systems.

Copper (Cu) is an important transition metal, and its isotopes have important applications in geology, environmental science, soil science, and other fields. Cu isotope fractionation can occur in many natural processes. However, the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems is not very clear. In this study, the fractionation effects of complexes of Cu(I) and Cu(II) in solution/hydrothermal solution systems were systematically studied by means of an ab initio method based on first principles. In the simulation of an aqueous solution system, the theoretical treatment method used is the "water-droplet" method. The results show that the heavy Cu isotope (65Cu) enrichment capacity of the Cu-bearing complex solutions is greatly affected by the ligand types both for Cu(I) and Cu(II). For Cu(I) complex solutions, the heavy Cu isotope enrichment sequence is [Cu(HS)2]-·(H2O)42 > [Cu(HS)(H2O)]·(H2O)42 ≈ [Cu(HS)(H2S)]·(H2O)42 > [CuCl]·(H2O)42 > [CuCl2]-·(H2O)42 > [CuCl3]2-·(H2O)42. For the aqueous solutions of Cu(II) with an inorganic ligand (such as H2O, OH-, NO3-, SO42- and CN-), the order of heavy Cu isotope enrichment is as follows: [Cu(H2O)6]2+·(H2O)42 > [Cu(NO3)2]·(H2O)42 > [Cu(OH)2]·(H2O)42 > [CuSO4(H2O)3]·(H2O)42 > [CuNO3(H2O)4]+·(H2O)42 > [CuCN]+·(H2O)42. For the Cu(II) complex solutions with a halogen as ligands, the change order of 1000lnβ is [CuCl]+·(H2O)42 > [CuCl2]·(H2O)42 > [CuBr2]·(H2O)42 > [CuCl3]-·(H2O)42. The sequence of 1000lnβ for Cu(II) organic complex aqueous solutions is [Cu(HOC6H4COO)]+·(H2O)42 > [Cu(CH3CH2COO)]+·(H2O)42 > [Cu(COOHCOO)]+·(H2O)42. The calculation also found that for Cu(I) complex aqueous solutions, the difference in Cu isotope fractionation parameters (1000lnβ) between [CuCl2]-·(H2O)42 and [Cu(HS)2]-·(H2O)42 is relatively large. At 100 °C, the 1000lnβ of the two species are 1.14 and 1.55 (‱), respectively. The difference between the two could be reached up to 0.41 (‱). The Cu isotope fractionation parameter obtained with the "water droplet" method is also very different from the results of previous studies, which indicate that the Cu isotope fractionation behavior of the two is similar. At the same time, the exciting discovery is that the enrichment capacity of heavy Cu isotopes is significantly different between Cu(I) complex aqueous solutions and Cu(II) complex aqueous solutions. At 100 °C, the 1000lnβ of 6 Cu(I) complex aqueous solutions and 13 Cu(II) complex aqueous solutions ranged from 0.90 to 1.55 and 2.24 to 3.25(‱), respectively. It also shows that the REDOX reaction has a significant effect on the Cu isotope fractionation, especially in ore-forming fluids. Therefore, the ligand type is a factor that cannot be ignored when considering the mechanism of Cu isotope fractionation in solution/hydrothermal solution systems. Whether the solvation effect of an aqueous solution is considered or not has a great influence on the numerical values of the final Cu isotope fractionation factors. Hence, the solvation effect of an aqueous solution is an essential determinant in the theoretical calculation of the Cu isotope fractionation factors for Cu-bearing complex solutions.

Rhizobium symbiosis improves amino acid and secondary metabolite biosynthesis of tungsten-stressed soybean (Glycine max).

The industrially important transition metal tungsten (W) shares certain chemical properties with the essential plant micronutrient molybdenum and inhibits the activity of molybdoenzymes such as nitrate reductase, impacting plant growth. Furthermore, tungsten appears to interfere with metabolic processes on a much wider scale and to trigger common heavy metal stress response mechanisms. We have previously found evidence that the tungsten stress response of soybeans (Glycine max) grown with symbiotically associated N2-fixing rhizobia (Bradyrhizobium japonicum) differs from that observed in nitrogen-fertilized soy plants. This study aimed to investigate how association with symbiotic rhizobia affects the primary and secondary metabolite profiles of tungsten-stressed soybean and whether changes in metabolite composition enhance the plant's resilience to tungsten. This comprehensive metabolomic and proteomic study presents further evidence that the tungsten-stress response of soybean plants is shaped by associated rhizobia. Symbiotically grown plants (N fix) were able to significantly increase the synthesis of an array of protective compounds such as phenols, polyamines, gluconic acid, and amino acids such as proline. This resulted in a higher antioxidant capacity, reduced root-to-shoot translocation of tungsten, and, potentially, also enhanced resilience of N fix plants compared to non-symbiotic counterparts (N fed). Taken together, our study revealed a symbiosis-specific metabolic readjustment in tungsten-stressed soybean plants and contributed to a deeper understanding of the mechanisms involved in the rhizobium-induced systemic resistance in response to heavy metals.

Activation of CzcS/CzcR during zinc excess regulates copper tolerance and pyochelin biosynthesis of Pseudomonas aeruginosa.

CzcS/CzcR is a two-component system that has been found to modulate zinc homeostasis, quorum sensing, and antibiotic resistance in Pseudomonas aeruginosa. To fully understand the physiological functions of CzcS/CzcR, we performed a comparative transcriptome analysis in this study and discovered that CzcS/CzcR controls global gene expression when it is activated during zinc excess. In particular, we demonstrated that CzcS/CzcR is critical for maintaining copper tolerance and iron homeostasis, which are disrupted during zinc excess, by inducing the expression of the copper tolerance gene ptrA and repressing the pyochelin biosynthesis genes through pchR. This study revealed the global regulatory functions of CzcS/CzcR and described a new and intricate adaptive mechanism in response to zinc excess in P. aeruginosa. The findings of this study have important implications for novel anti-infective interventions by incorporating metal-based drugs.

Titanium in photocatalytic organic transformations: current applications and future developments.

Titanium, as an important transition metal, has garnered extensive attention in both industry and academia due to its excellent mechanical properties, corrosion resistance, and unique reactivity in organic synthesis. In the field of organic photocatalysis, titanium-based compounds such as titanium dioxide (TiO2), titanocenes (Cp2TiCl2, CpTiCl3), titanium tetrachloride (TiCl4), tetrakis(isopropoxy)titanium (Ti(OiPr)4), and chiral titanium complexes have demonstrated distinct reactivity and selectivity. This review focuses on the roles of these titanium compounds in photocatalytic organic reactions, and highlights the reaction pathways such as photo-induced single-electron transfer (SET) and ligand-to-metal charge transfer (LMCT). By systematically surveying the latest advancements in titanium-involved organic photocatalysis, this review aims to provide references for further research and technological innovation within this fast-developing field.

A Ratiometric Fluorescent Sensor Based on Chelation-Enhanced Fluorescence of Carbon Dots for Zinc Ion Detection

Zinc ion, one of the most important transition metal ions in living organisms, plays a crucial role in the homeostasis of the organism. The disorder of zinc is associated with many major diseases. It is highly desirable to develop selective and sensitive methods for the real-time detection of zinc ions. In this work, double-emitting fluorescent carbon dots (CDs) are prepared by a solvothermal method using glutathione, L-aspartic acid, and formamide as the raw materials. The carbon dots specifically recognize zine ions and produce a decrease in fluorescence intensity at 684 nm and an increase at 649 nm, leading to a ratiometric fluorescent sensor for zinc detection. Through surface modification and spectral analysis, the surface groups including carboxyl, carbonyl, hydroxyl, and amino groups, and C=N in heterocycles of CDs are revealed to synergistically coordinate Zn2+, inducing the structural changes in the emission site. The CDs can afford a low limit of detection of ~5 nM for Zn2+ detection with good linearity in the range of 0.02–5 μM, showing good selectivity as well. The results from real samples including fetal bovine serum, milk powder, and zinc gluconate oral solution indicated the good applicability of the CDs in the determination of Zn2+.

New Insight on the Formation of 2-Aminoacetophenone in White Wines

This study aimed to improve the understanding of 2-aminoacetophenone (2-AAP) formation in white wines, a compound responsible for atypical ageing (ATA) associated with a rapid loss of white wine fruity aroma and to the development of unpleasant odors. Two surveys performed in 139 white wines from Central Europe investigated the varietal effect on wine tendency to form 2-AAP during ageing. The role of some antioxidants and important transition metal ions present in wine (Fe, Cu and Mn) in the formation of 2-AAP was also investigated. The surveys highlighted that Muscat and Riesling wines showed significantly higher concentrations of 2-AAP than Chardonnay and some other regional varieties found in Central Europe such as Grüner Veltliner, Welschriesling and Zelen. The origin of such varietal effects could not be related to the level of any 2-AAP precursor. On the other hand, some of the important wine matrix effects were highlighted. A certain variability in capacity of different antioxidants to limit 2-AAP formation was observed. Supplementations of commercial tannins in wines tended to be more efficient than glutathione in preserving wines from the formation of 2-AAP. Transition metal ions significantly impacted 2-AAP synthesis through complex interactions. Generally, Fe and Mn tended to promote formation of 2-AAP, while the presence of Cu limited it. The higher concentration of transition metal ions significantly improved the efficiency of antioxidants to reduce 2-AAP formation. Further studies investigating the origin of varietal effects and the complex matrix effects involving metal ions and antioxidants in 2-AAP production are warranted.

Enhanced thermoelectric performance of MoS2-Bi2S3 nanocomposites via low energy carrier filtering effect

Layered MoS2 (Molybdenum disulphide), an important transition metal dichalcogenide for energy conversion application due to intrinsic low thermal conduction and attractive functional properties. Here, we report on the hydrothermally prepared MoS2/Bi2S3 nanocomposites for mid-temperature thermoelectric applications. X-ray photo electron Spectroscopy reveals the change in fermi level of nanocomposites with Bi incorporation and oxidation states of the elements. High-Resolution Transmission Electron Microscope (HR-TEM) clearly indicates the formation of MoS2 nanosheets and Bi2S3 nano wires with the presence of interfaces. The interfacial effect greatly improved the thermoelectric power factor of 900 nW/mK2, which is nearly 8 times higher than pure MoS2.

Electrospun membranes of iron tailings toward peroxymonosulfate activation for efficient photocatalytic degradation of organic pollutants

Iron-based catalysts are considered to be an important and promising transition metal catalyst. However, although the developed iron-based catalysts have good catalytic activity for peroxymonosulfate (PMS), their complex synthesis process, high cost and difficult recovery limit their large-scale application. In this work, a high performance, environmentally friendly and easily recyclable catalyst was prepared by anchoring iron tailings into electrospun fibers (EF). The electrospun membranes of iron tailings (EF-iron tailings) could activate PMS for degradation of organic pollutants under visible light. During reaction process, visible light accelerated the valence state transition of iron, which was conducive to the activation of PMS. The degradation mechanism showed that hydroxyl radical (·OH), superoxide radical (·O2−) and singlet oxygen (1O2) were the main active species, and·O2− and 1O2 seemed to be more important for degradation. The application assessment in natural water confirmed potential practical application value of the EF-iron tailings membrane. The leaching test showed that the iron leaching amount of the EF-iron tailings membrane was low in the reaction process, meeting environmental requirements. This work provides an effective green preparation strategy of efficient solid waste-based catalyst with pro-environment and easy recycling.

An ESIPT solvatochromic fluorescent and colorimetric probe for sensitive and selective detection of copper ions in environmental samples and cell lines.

Copper is one of the most important transition metals in our body for various physiological functions. An imbalance in the homeostasis of copper in our body can lead to various neurological disorders such as Alzheimer's disease, Parkinson's, and Menkes disease. As a result, there is a need for the detection of excess copper present in the environment and the human system. In this work, we have designed a quinoline-based fluorescent/colorimetric probe (QHS) for rapid and selective detection of copper ions via quenching of fluorescence/color change from yellow to peach which is visible to the naked eye. The probe displayed high selectivity towards copper(II), i.e., Cu(II) in the presence of different metal analytes in water samples. The sensing mechanism of the probe was confirmed by NMR, HRMS, IR spectroscopy, and SEM. The detection limit of Cu(II) ions was found to be 0.493 μM which is lower than the tolerable limit of copper (20 μM) in drinking water as per the EPA. The probe was also utilized for the visualization of Cu(II) in cell lines. The probe was also demonstrated for its application in real-time detection of aqueous samples using portable paper strips.

Concentration-dependent effect of Nickel ions on amyloid fibril formation kinetics of hen egg white lysozyme: A Raman spectroscopy study

Nickel, an important transition metal element, is one of the trace elements for human body and has a crucial impact on life and health. Some evidences show the excess exposure to metal ions might be associated with neurological diseases. Herein, we applied Raman spectroscopy to study the Ni(II) ion effect on kinetics of amyloid fibrillation of hen egg white lysozyme (HEWL) in thermal and acidic conditions. Using the well-known Raman indicators for protein tertiary and secondary structures, we monitored and analyzed the concentration effect of Ni(II) ions on the unfolding of tertiary structures and the transformation of secondary structures. The experimental evidence validates the accelerator role of the metal ion in the kinetics. Notably, the additional analysis of the amide I band profile, combined with thioflavin-T fluorescence assays, clearly indicates the inhibitory effect of Ni(II) ions on the formation of amyloid fibrils with organized β-sheets structures. Instead, a more significant promotion influence is affirmed on the assembly into other aggregates with disordered structures. The present results provide rich information about the specific metal-mediated protein fibrillation.

A colorimetric and fluorometric dual-mode carbon dots probe derived from phenanthroline precursor for the selective detection of Fe2+ and Fe3.

Iron's metabolism is heavily involved in the regulation of redox balance for cell functions, however, the simultaneous monitoring of Fe2+/3+ concentration is still a great challenge due to their transitional nature in biological systems. A novel type of carbon dots (CDs) was synthesized by solvothermal treatment with 5-amino-1,10-phenanthroline (Aphen) and salicylic acid as precursors, and the resulting targeted CDs (T-CDs) were used to simultaneously detect Fe2+ and Fe3+. Comprehensive experimental characterizations revealed that the strong binding affinity of Aphen moiety to Fe2+ leads to the formation of rigid T-CDs aggregates, which causes a substantial enhancement of fluorescence intensity, whereas Fe3+ could cause the fluorescence quenching of T-CDs due to the oxidation-reduction induced electron transfer. These different fluorescence responses allow T-CDs to sensitively differentiate Fe2+ from Fe3+, and give the limit of detection (LOD) of 1.78 and 2.78μM for Fe2+ and Fe3+, respectively. Furthermore, the Aphen dominated structure endows the T-CDs with a colorimetric response to Fe2+ with a LOD of 0.13μM, which is very different from Fe3+. Thus, the dynamic changes of Fe2+ and Fe3+ in solution can be accurately monitored by T-CDs within the total iron concentration of 50μM, which is probably the most sensitive dual-mode probe reported so far. In addition, this probe is successfully applied to detect the Fe2+/3+ concentration in cells, demonstrating a huge application potential in the sensing of the dynamic equilibrium of these important transition metals during the cell metabolism or stimulated process. The dynamic changes of Fe2+ and Fe3+ in solution can be accurately monitored by carbon dots based on the colorimetric and fluorometric dual-mode.

Effects of exogenous Fe addition on soil respiration rate and dissolved organic carbon structure in temperate forest swamps of northeastern China

Fe as an important redox-active transition metal plays a key role in the carbon cycle of ecosystems. To date, the mechanisms by which Fe affects organic carbon (soil respiration rate [Rs] and dissolved organic carbon [DOC] structure) remain unclear, because most studies only focused on the effect of Fe on soil organic carbon content. To understand these effects, a 30-day laboratory incubation experiment was conducted using forest swamp soils from northeastern China amended with different concentrations of exogenous Fe (no exogenous Fe added [L0], add exogenous Fe at 1 time the soil background value [L1], add exogenous Fe at 2 times the soil background value [L2]). Our results showed that exogenous Fe addition reduced the soil respiration rate by 54.8% during the incubation time. The DOC concentration decreased by 40.5% with exogenous Fe addition during the incubation time. The dissolved organic matter (DOM) characteristic parameters showed apparent variations (p < 0.05), including significant increases in the fluorescence and biological index and significant decreases in the humification index, which indicate that exogenous Fe addition reduced humification, which may lead to the increased fixation of dissolved organic carbon. In addition significant increases in tryptophan-like DOM was observed when exogenous Fe addition resulted in a soil Fe concentration of twice the background value (p < 0.05). These findings indicate that exogenous Fe addition promotes the production of endogenous soil DOC by microorganisms. Overall, Our study uses three-dimensional fluorescence spectroscopy techniques combined with the parallel factor analysis (PARAFAC) to characterize the dissolved organic matter components in soil samples under exogenous Fe addition conditions, with a view to exploring the differences in the effects of Fe on the DOC concentration and structure of wetland soils, providing a theoretical basis for the mechanisms of soil carbon fixation and soil organic matter transformation in wetland soils.

Interactions of Isoquinoline Alkaloids with Transition Metals Iron and Copper.

Data on alkaloid interactions with the physiologically important transition metals, iron and copper, are mostly lacking in the literature. However, these interactions can have important consequences in the treatment of both Alzheimer’s disease and cancer. As isoquinoline alkaloids include galanthamine, an approved drug for Alzheimer’s disease, as well as some potentially useful compounds with cytostatic potential, 28 members from this category of alkaloids were selected for a complex screening of interactions with iron and copper at four pathophysiologically relevant pH and in non-buffered conditions (dimethyl sulfoxide) by spectrophotometric methods in vitro. With the exception of the salts, all the alkaloids were able to chelate ferrous and ferric ions in non-buffered conditions, but only five of them (galanthine, glaucine, corydine, corydaline and tetrahydropalmatine) evoked some significant chelation at pH 7.5 and only the first two were also active at pH 6.8. By contrast, none of the tested alkaloids chelated cuprous or cupric ions. All the alkaloids, with the exception of the protopines, significantly reduced the ferric and cupric ions, with stronger effects on the latter. These effects were mostly dependent on the number of free aromatic hydroxyls, but not other hydroxyl groups. The most potent reductant was boldine. As most of the alkaloids chelated and reduced the ferric ions, additional experimental studies are needed to elucidate the biological relevance of these results, as chelation is expected to block reactive oxygen species formation, while reduction could have the opposite effect.

Ru incorporation for boosting Co3O4 oxidase-like activity in dopamine colorimetric detection

Co3O4 has emerged as an important transition metal oxide in imitating nature enzyme, but it affords low oxidase mimetic activity. Herein, Ru doping has been utilized to modulate Co3O4 oxidase-like activity. Various Ru-doped Co3O4 nanoparticles (RuxCo3-xO4 NPs, x ≤ 0.3) were prepared and utilized as oxidase mimic to trigger 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation. The catalytic performance varies with Ru incorporation, and Ru0.3Co2.7O4 NPs shows the highest oxidase mimetic activity. In comparison with Co3O4 NPs, Ru0.3Co2.7O4 NPs displays 2.8-fold lower Km yet 14.3-fold higher catalytic efficiency. As a highly efficient oxidase mimic, Ru0.3Co2.7O4 NPs holds promising in setting up colorimetric sensing platform for biomolecule dopamine (DA) detection. This work provides guidance for regulating Co3O4 oxidase mimic via simple Ru doping, and establishes a facile colorimetric sensing method for DA.

Integrated metabolomics revealed the fibromyalgia-alleviation effect of Mo2C nanozyme through regulated homeostasis of oxidative stress and energy metabolism

Fibromyalgia (FM), the most common cause of chronic musculoskeletal pain in the general public, lacks advanced therapeutic methodology and detailed bioinformation. However, acting as a newly developed and important transition metal carbide or carbonitride, the Mo2C nanozyme has provided a novel iatrotechnique with excellent bioactivity in a cell/animal model, which also exhibits potential prospects for future clinical applications. In addition, high-content and high-throughput integrated metabolomics (including aqueous metabolomics, lipidomics, and desorption electrospray ionization-mass spectrometry imaging) also specializes in qualitative and quantitative analysis of metabolic shifts at the molecular level. In this work, the FM-alleviation effect of Mo2C nanozyme was investigated through integrated metabolomics in a mouse model. An advanced platform combining gas chromatography-mass spectrometry, liquid chromatography-mass spectrometry and bioinformatics was utilized to study the variation in the mouse metabolome and lipidome. The results revealed that Mo2C treatment could effectively enhance energy metabolism-related biological events impaired by FM, leading to homeostasis of oxidative stress and energy metabolism toward the control levels. During this process, Mo2C facilitated the elimination of ROS in plasma and cells and the rehabilitation of mice from oxidative stress and mitochondrial dysfunction. It was believed that such an integrated metabolomics study on the FM-alleviation effect of Mo2C nanozyme could provide another excellent alternative to traditional Mo2C-based research with numerous pieces of bioinformation, further supporting research area innovation, material modification, and clinical application.

Directional Growth of Conductive Metal-Organic Framework Nanoarrays along [001] on Metal Hydroxides for Aqueous Asymmetric Supercapacitors.

Metal-organic frameworks (MOFs) are promising electrochemical materials that possess large specific surface areas, high porosities, good adjustability, and high activities. However, many conventional MOFs exhibit poor conductivity, which hinders their application in electrochemistry. In recent years, conductive MOFs (cMOFs) have attracted a considerable attention. As an important transition metal hydroxide, Ni(OH)2 nanosheets exhibit a high theoretical specific capacitance and a high energy density but a poor electrical conductivity. In this study, we combined a typical cMOF(Ni-HHTP, HHTP = 2,3,6,7,10,11-hexahydroxybenzene) with Ni(OH)2 nanosheets and synthesized a series of Ni-HHTP@Ni(OH)2 nanoarrays. The composite materials exhibit a high electrical conductivity and ionic transfer efficiency and a good stability. Most importantly, our study reveals the chemical interaction between cMOFs and metal hydroxide composites and the relationship between facet exposure and the growth orientation of cMOFs. When Ni-HHTP@Ni(OH)2-2 was assembled as a positive electrode material in an aqueous asymmetric supercapacitor, 98% of the initial capacitance was maintained after 5000 cycles at a high current density of 3 A g-1. The findings of this study will provide meaningful insights into the design of cMOF composites combining other metal hydroxides.

Investigation of the Tetrakis(dimethylamino)hafnium and H2S ALD Process: Effects of Deposition Temperature and Annealing

HfS2 has recently emerged as a promising 2D semiconductor, but the lack of a reliable method to produce continuous films on a large scale has hindered its spreading. The atomic layer deposition of the material with the precursor tetrakis-dimethylamino-hafnium with H2S is a relatively novel solution to this problem. This paper shows that it is a facile approach to synthesizing homogeneous and smooth HfS2 layers in a controlled and reproducible manner. The deposition is examined at different temperatures and layer thicknesses, exploring the ALD window of the deposition and the chemical, morphological and electronic properties of the films. The method yielded films with wafer-sized uniformity and controlled properties and is, thus, a promising way to prepare this important transition metal dichalcogenide material.

Wafer-Scalable Single-Layer Amorphous Molybdenum Trioxide.

Molybdenum trioxide (MoO3), an important transition metal oxide (TMO), has been extensively investigated over the past few decades due to its potential in existing and emerging technologies, including catalysis, energy and data storage, electrochromic devices, and sensors. Recently, the growing interest in two-dimensional (2D) materials, often rich in interesting properties and functionalities compared to their bulk counterparts, has led to the investigation of 2D MoO3. However, the realization of large-area true 2D (single to few atom layers thick) MoO3 is yet to be achieved. Here, we demonstrate a facile route to obtain wafer-scale monolayer amorphous MoO3 using 2D MoS2 as a starting material, followed by UV-ozone oxidation at a substrate temperature as low as 120 °C. This simple yet effective process yields smooth, continuous, uniform, and stable monolayer oxide with wafer-scale homogeneity, as confirmed by several characterization techniques, including atomic force microscopy, numerous spectroscopy methods, and scanning transmission electron microscopy. Furthermore, using the subnanometer MoO3 as the active layer sandwiched between two metal electrodes, we demonstrate the thinnest oxide-based nonvolatile resistive switching memory with a low voltage operation and a high ON/OFF ratio. These results (potentially extendable to other TMOs) will enable further exploration of subnanometer stoichiometric MoO3, extending the frontiers of ultrathin flexible oxide materials and devices.