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1. Gallionellaceae pangenomic analysis reveals insight into phylogeny, metabolic flexibility, and iron oxidation mechanisms

   https://doi.org/10.1128/msystems.00038-23  

   Hoover, Rene L. ; Keffer, Jessica L. ; Polson, Shawn W. ; Chan, Clara S. ( December 2023 , mSystems)

   Newton, Ryan J. (Ed.)

   The iron-oxidizing Gallionellaceae drive a wide variety of biogeochemical cycles through their metabolisms and biominerals. To better understand the environmental impacts of Gallionellaceae, we need to improve our knowledge of their diversity and metabolisms, especially any novel iron oxidation mechanisms. Here, we used a pangenomic analysis of 103 genomes to resolve Gallionellaceae phylogeny and explore their genomic potential. Using a concatenated ribosomal protein tree and key gene patterns, we determined Gallionellaceae has four genera, divided into two groups: iron-oxidizing bacteria (FeOB)Gallionella,Sideroxydans, andFerriphaseluswith iron oxidation genes (cyc2,mtoA) and nitrite-oxidizing bacteria (NOB)CandidatusNitrotoga with the nitrite oxidase genenxr. The FeOB and NOB have similar electron transport chains, including genes for reverse electron transport and carbon fixation. Auxiliary energy metabolisms, including S oxidation, denitrification, and organotrophy, were scattered throughout the FeOB. Within FeOB, we found genes that may represent adaptations for iron oxidation, including a variety of extracellular electron uptake mechanisms. FeOB genomes encoded more predictedc-type cytochromes than NOB genomes, notably more multihemec-type cytochromes (MHCs) with >10 CXXCH motifs. These include homologs of several predicted outer membrane porin-MHC complexes, including MtoAB and Uet. MHCs efficiently conduct electrons across longer distances and function across a wide range of redox potentials that overlap with mineral redox potentials, which can expand the range of usable iron substrates. Overall, the results of pangenome analyses suggest that the Gallionellaceae generaGallionella,Sideroxydans, andFerriphaselushave acquired a range of adaptations to succeed in various environments but are primarily iron oxidizers.

   Neutrophilic iron-oxidizing bacteria (FeOB) produce copious iron (oxyhydr)oxides that can profoundly influence biogeochemical cycles, notably the fate of carbon and many metals. To fully understand environmental microbial iron oxidation, we need a thorough accounting of iron oxidation mechanisms. In this study, we show the Gallionellaceae FeOB genomes encode both characterized iron oxidases as well as uncharacterized multiheme cytochromes (MHCs). MHCs are predicted to transfer electrons from extracellular substrates and likely confer metabolic capabilities that help Gallionellaceae occupy a range of different iron- and mineral-rich niches. Gallionellaceae appear to specialize in iron oxidation, so it would be advantageous for them to have multiple mechanisms to oxidize various forms of iron, given the many iron minerals on Earth, as well as the physiological and kinetic challenges faced by FeOB. The multiple iron/mineral oxidation mechanisms may help drive the widespread ecological success of Gallionellaceae.

    

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2. Oxygen Vacancy Introduction to Increase the Capacity and Voltage Retention in Li‐Excess Cathode Materials

   https://doi.org/10.1002/sstr.202200343  

   Huang, Jianping ; Zhong, Peichen ; Ha, Yang ; Lun, Zhengyan ; Tian, Yaosen ; Balasubramanian, Mahalingam ; Yang, Wanli ; Ceder, Gerbrand ( November 2022 , Small Structures)

   Li‐rich rocksalt oxides are promising cathode materials for lithium‐ion batteries due to their large capacity and energy density, and their ability to use earth‐abundant elements. The excess Li in the rocksalt, needed to achieve good Li transport, reduces the theoretical transition metal redox capacity and introduces a labile oxygen state, both of which lead to increased oxygen oxidation and concomitant capacity loss with cycling. Herein, it is demonstrated that substituting the labile oxygen in Li‐rich cation‐disordered rocksalt materials with a vacancy is an effective strategy to inhibit oxygen oxidation. It is found that the oxygen vacancy in cation‐disordered lithium manganese oxide favors high Li coordination thereby reducing the concentration of unhybridized oxygen states, while increasing the theoretical Mn capacity. It is shown that in the vacancy‐containing compound, synthesized by ball milling, the Mn valence is lowered to less than +3, providing access to more than 300 mAh g⁻¹capacity from the Mn²⁺/Mn⁴⁺redox reservoir. The increased transition metal redox and decreased O oxidation are found to improve the capacity and voltage retention, indicating that oxygen vacancy creation to remove the most vulnerable oxygen ions and reduce transition metal valence provides a new opportunity for the design of high‐performance Li‐rich rocksalt cathodes.

    

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3. The effect of intrinsic layer on the performance of oxide-based p-i-n heterojunctions integrating p-SnOx and n-InGaZnO

   Lee, Dong Hun ; Lee, Sunghwan ( May 2022 , Materials Research Society)

   The discovery of oxide electronics is of increasing importance today as one of the most promising new technologies and manufacturing processes for a variety of electronic and optoelectronic applications such as next-generation displays, batteries, solar cells, and photodetectors. The high potential use seen in oxide electronics is due primarily to their high carrier mobilities and their ability to be fabricated at low temperatures. However, since the majority of oxide semiconductors are n-type oxides, current applications are limited to unipolar devices, eventually developing oxide-based bipolar devices such as p-n diodes and complementary metal-oxide semiconductors. We have contributed to wide range of oxide semiconductors and their electronics and optoelectronic device applications. Particularly, we have demonstrated n-type oxide-based thin film transistors (TFT), integrating In2O3-based n-type oxide semiconductors from binary cation materials to ternary cation species including InZnO, InGaZnO (IGZO), and InAlZnO. We have suggested channel/metallization contact strategies to achieve stable TFT performance, identified vacancy-based native defect doping mechanisms, suggested interfacial buffer layers to promote charge injection capability, and established the role of third cation species on the carrier generation and carrier transport. More recently, we have reported facile manufacturing of p-type SnOx through reactive magnetron sputtering from a Sn metal target. The fabricated p-SnOx was found to be devoid of metallic phase of Sn from x-ray photoelectron spectroscopy and demonstrated stable performance in a fully oxide based p-n heterojunction together with n-InGaZnO. The oxide-based p-n junctions exhibited a high rectification ratio greater than 103 at ±3 V, a low saturation current of ~2x10-10, and a small turn-on voltage of -0.5 V. With all the previous achievements and investigations about p-type oxide semiconductors, challenges remain for implementing p-type oxide realization. For the implementation of oxide-based p-n heterojunctions, the performance needs to be further enhanced. The current on/off ration may be limited, in our device structure, due to either high reverse saturation current (or current density) or non-ideal performance. In this study, two rational strategies are suggested to introduce an “intrinsic” layer, which is expected to reduce the reverse saturation current between p-SnOx and n-IGZO and hence increase the on/off ratio. The carrier density of n-IGZO is engineered in-situ during the sputtering process, by which compositionally homogeneous IGZO with significantly reduced carrier density is formed at the interface. Then, higher carrier density IGZO is formed continuously on the lower carrier density IGZO during the sputtering process without any exposure of the sample to the air. Alternatively, heterogeneous oxides of MgO and SiO2 are integrated into between p-SnOx and n-IGZO, by which the defects on the surface can be passivated. The interfacial properties are thoroughly investigated using transmission electron microscopy and atomic force microscopy. The I-V characteristics are compared between the set of devices integrated with two types of “intrinsic” layers. The current research results are expected to contribute to the development of p-type oxides and their industrial application manufacturing process that meets current processing requirements, such as mass production in p-type oxide semiconductors. 

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4. (Invited) Oxide Electronics and Recent Progress in Bipolar Applications

   https://doi.org/10.1149/MA2022-01191071mtgabs  

   Lee, Sunghwan ; Lee, Donghun ; Qin, Fei ; Zhang, Yuxuan ; Rothschild, Molly ; Song, Han Wook ; No, Kwangsoo ( July 2022 , ECS Meeting Abstracts)

   The discovery of oxide electronics is of increasing importance today as one of the most promising new technologies and manufacturing processes for a variety of electronic and optoelectronic applications such as next-generation displays, batteries, solar cells, memory devices, and photodetectors[1]. The high potential use seen in oxide electronics is due primarily to their high carrier mobilities and their ability to be fabricated at low temperatures[2]. However, since the majority of oxide semiconductors are n-type oxides, current applications are limited to unipolar devices, eventually developing oxide-based bipolar devices such as p-n diodes and complementary metal-oxide semiconductors. We have contributed to a wide range of oxide semiconductors and their electronics and optoelectronic device applications. Particularly, we have demonstrated n-type oxide-based thin film transistors (TFT), integrating In 2 O 3 -based n-type oxide semiconductors from binary cation materials to ternary cation species including InZnO, InGaZnO (IGZO), and InAlZnO. We have suggested channel/metallization contact strategies to achieve stable and high TFT performance[3, 4], identified vacancy-based native defect doping mechanisms[5], suggested interfacial buffer layers to promote charge injection capability[6], and established the role of third cation species on the carrier generation and carrier transport[7]. More recently, we have reported facile manufacturing of p-type SnOx through reactive magnetron sputtering from a Sn metal target[8]. The fabricated p-SnOx was found to be devoid of metallic phase of Sn from x-ray photoelectron spectroscopy and demonstrated stable performance in a fully oxide-based p-n heterojunction together with n-InGaZnO. The oxide-based p-n junctions exhibited a high rectification ratio greater than 10 3 at ±3 V, a low saturation current of ~2x10 -10 , and a small turn-on voltage of -0.5 V. In this presentation, we review recent achievements and still remaining issues in transition metal oxide semiconductors and their device applications, in particular, bipolar applications including p-n heterostructures and complementary metal-oxide-semiconductor devices as well as single polarity devices such as TFTs and memristors. In addition, the fundamental mechanisms of carrier transport behaviors and doping mechanisms that govern the performance of these oxide-based devices will also be discussed. ACKNOWLEDGMENT This work was supported by the U.S. National Science Foundation (NSF) Award No. ECCS-1931088. S.L. and H.W.S. acknowledge the support from the Improvement of Measurement Standards and Technology for Mechanical Metrology (Grant No. 20011028) by KRISS. K.N. was supported by Basic Science Research Program (NRF-2021R11A1A01051246) through the NRF Korea funded by the Ministry of Education. REFERENCES [1] K. Nomura et al. , Nature, vol. 432, no. 7016, pp. 488-492, Nov 25 2004. [2] D. C. Paine et al. , Thin Solid Films, vol. 516, no. 17, pp. 5894-5898, Jul 1 2008. [3] S. Lee et al. , Journal of Applied Physics, vol. 109, no. 6, p. 063702, Mar 15 2011, Art. no. 063702. [4] S. Lee et al. , Applied Physics Letters, vol. 104, no. 25, p. 252103, 2014. [5] S. Lee et al. , Applied Physics Letters, vol. 102, no. 5, p. 052101, Feb 4 2013, Art. no. 052101. [6] M. Liu et al. , ACS Applied Electronic Materials, vol. 3, no. 6, pp. 2703-2711, 2021/06/22 2021. [7] A. Reed et al. , Journal of Materials Chemistry C, 10.1039/D0TC02655G vol. 8, no. 39, pp. 13798-13810, 2020. [8] D. H. Lee et al. , ACS Applied Materials & Interfaces, vol. 13, no. 46, pp. 55676-55686, 2021/11/24 2021. 

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5. Modeling surface spin polarization on ceria-supported Pt nanoparticles

   https://doi.org/10.1088/1361-648X/ac62a3  

   Kang, Byungkyun ; Vincent, Joshua L ; Lee, Yongbin ; Ke, Liqin ; Crozier, Peter A ; Zhu, Qiang ( April 2022 , Journal of Physics: Condensed Matter)

   Abstract In this work, we employ density functional theory simulations to investigate possible spin polarization of CeO 2 -(111) surface and its impact on the interactions between a ceria support and Pt nanoparticles. With a Gaussian type orbital basis, our simulations suggest that the CeO 2 -(111) surface exhibits a robust surface spin polarization due to the internal charge transfer between atomic Ce and O layers. In turn, it can lower the surface oxygen vacancy formation energy and enhance the oxide reducibility. We show that the inclusion of spin polarization can significantly reduce the major activation barrier in the proposed reaction pathway of CO oxidation on ceria-supported Pt nanoparticles. For metal-support interactions, surface spin polarization enhances the bonding between Pt nanoparticles and ceria surface oxygen, while CO adsorption on Pt nanoparticles weakens the interfacial interaction regardless of spin polarization. However, the stable surface spin polarization can only be found in the simulations based on the Gaussian type orbital basis. Given the potential importance in the design of future high-performance catalysts, our present study suggests a pressing need to examine the surface ferromagnetism of transition metal oxides in both experiment and theory. 

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