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Showing papers by "National Institute of Advanced Industrial Science and Technology published in 2020"


Journal ArticleDOI
28 Jan 2020-ACS Nano
TL;DR: Prominent authors from all over the world joined efforts to summarize the current state-of-the-art in understanding and using SERS, as well as to propose what can be expected in the near future, in terms of research, applications, and technological development.
Abstract: The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.

1,768 citations


Journal ArticleDOI
27 May 2020-Nature
TL;DR: Water splitting with an internal quantum efficiency of almost unity is achieved using a modified semiconductor photocatalyst that selectively promotes the hydrogen and oxygen evolution reactions on separate crystal facets, reaching the upper limit of quantum efficiency for overall water splitting.
Abstract: Overall water splitting, evolving hydrogen and oxygen in a 2:1 stoichiometric ratio, using particulate photocatalysts is a potential means of achieving scalable and economically viable solar hydrogen production. To obtain high solar energy conversion efficiency, the quantum efficiency of the photocatalytic reaction must be increased over a wide range of wavelengths and semiconductors with narrow bandgaps need to be designed. However, the quantum efficiency associated with overall water splitting using existing photocatalysts is typically lower than ten per cent1,2. Thus, whether a particulate photocatalyst can enable a quantum efficiency of 100 per cent for the greatly endergonic water-splitting reaction remains an open question. Here we demonstrate overall water splitting at an external quantum efficiency of up to 96 per cent at wavelengths between 350 and 360 nanometres, which is equivalent to an internal quantum efficiency of almost unity, using a modified aluminium-doped strontium titanate (SrTiO3:Al) photocatalyst3,4. By selectively photodepositing the cocatalysts Rh/Cr2O3 (ref. 5) and CoOOH (refs. 3,6) for the hydrogen and oxygen evolution reactions, respectively, on different crystal facets of the semiconductor particles using anisotropic charge transport, the hydrogen and oxygen evolution reactions could be promoted separately. This enabled multiple consecutive forward charge transfers without backward charge transfer, reaching the upper limit of quantum efficiency for overall water splitting. Our work demonstrates the feasibility of overall water splitting free from charge recombination losses and introduces an ideal cocatalyst/photocatalyst structure for efficient water splitting. Water splitting with an internal quantum efficiency of almost unity is achieved using a modified semiconductor photocatalyst that selectively promotes the hydrogen and oxygen evolution reactions on separate crystal facets.

971 citations


Journal ArticleDOI
TL;DR: A wide range of applications based on these materials for ORR, OER, HER and multifunctional electrocatalysis are discussed, with an emphasis on the required features of MOF-derived carbon-based materials for the Electrocatalysis of corresponding reactions.
Abstract: Oxygen reduction reaction (ORR), oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) are three key reactions for the development of green and sustainable energy systems. Efficient electrocatalysts for these reactions are highly desired to lower their overpotentials and promote practical applications of related energy devices. Metal–organic frameworks (MOFs) have recently emerged as precursors to fabricate carbon-based electrocatalysts with high electrical conductivity and uniformly distributed active sites. In this review, the current progress of MOF-derived carbon-based materials for ORR/OER/HER electrocatalysis is presented. Materials design strategies of MOF-derived carbon-based materials are firstly summarized to show the rich possibilities of the morphology and composition of MOF-derived carbon-based materials. A wide range of applications based on these materials for ORR, OER, HER and multifunctional electrocatalysis are discussed, with an emphasis on the required features of MOF-derived carbon-based materials for the electrocatalysis of corresponding reactions. Finally, perspectives on the development of MOF-derived carbon-based materials for ORR, OER and HER electrocatalysis are provided.

970 citations



Journal ArticleDOI
TL;DR: This review focuses on the design and fabrication of one-, two- and three-dimensional MOFs at micro/nanoscale, and their direct applications in batteries, supercapacitors and electrocatalysis.
Abstract: As a new class of crystalline porous materials, metal-organic frameworks (MOFs) have received great attention owing to their unique advantages of ultrahigh surface area, large pore volume and versatile applications. Developing different strategies to control the morphology and size of MOFs is very important for their practical applications. Recently, micro/nanosized MOFs have been regarded as promising candidates for electrode materials with excellent performances, which not only bridge the gap between fundamental MOF science and forward-looking applications, but also provide an opportunity to make clear the relationship between morphologies and properties. This review focuses on the design and fabrication of one-, two- and three-dimensional MOFs at micro/nanoscale, and their direct applications in batteries, supercapacitors and electrocatalysis. A discussion on challenges and future prospects of the synthesis and electrochemical applications of micro/nanoscaled MOF materials is presented.

615 citations


Journal ArticleDOI
TL;DR: A discussion of many of the recently implemented features of GAMESS (General Atomic and Molecular Electronic Structure System) and LibCChem (the C++ CPU/GPU library associated with GAMESS) is presented, which include fragmentation methods, hybrid MPI/OpenMP approaches to Hartree-Fock, and resolution of the identity second order perturbation theory.
Abstract: A discussion of many of the recently implemented features of GAMESS (General Atomic and Molecular Electronic Structure System) and LibCChem (the C++ CPU/GPU library associated with GAMESS) is presented. These features include fragmentation methods such as the fragment molecular orbital, effective fragment potential and effective fragment molecular orbital methods, hybrid MPI/OpenMP approaches to Hartree-Fock, and resolution of the identity second order perturbation theory. Many new coupled cluster theory methods have been implemented in GAMESS, as have multiple levels of density functional/tight binding theory. The role of accelerators, especially graphical processing units, is discussed in the context of the new features of LibCChem, as it is the associated problem of power consumption as the power of computers increases dramatically. The process by which a complex program suite such as GAMESS is maintained and developed is considered. Future developments are briefly summarized.

575 citations


Journal ArticleDOI
TL;DR: This review overviews the recent developments of catalysis at single metal sites in MOF-based materials with emphasis on their structures and applications for thermocatalysis, electrocatalysis, and photocatalysis.
Abstract: Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, and high surface area, different types of MOF-based single metal sites are well exploited, including coordinately unsaturated metal sites from metal nodes and metallolinkers, as well as active metal species immobilized to MOFs. Furthermore, controllable thermal transformation of MOFs can upgrade them to nanomaterials functionalized with active single-atom catalysts (SACs). These unique features of MOFs and their derivatives enable them to serve as a highly versatile platform for catalysis, which has actually been becoming a rapidly developing interdisciplinary research area. In this review, we overview the recent developments of catalysis at single metal sites in MOF-based materials with emphasis on their structures and applications for thermocatalysis, electrocatalysis, and photocatalysis. We also compare the results and summarize the major insights gained from the works in this review, providing the challenges and prospects in this emerging field.

571 citations


Journal ArticleDOI
01 May 2020
TL;DR: In this paper, the authors present a critical overview on the recent progress of the use of MOF-based materials for gaseous fuel storage, chemical hydrogen storage, solar and electrochemical energy storage and conversion.
Abstract: Metal–organic frameworks (MOFs), an emerging class of porous materials, have shown intriguing and promising properties in a wide range of applications due to their versatile structures, large surface areas, tunable porosity and tailorable chemistry. In recent years one of the most active research fields is to explore energy applications of MOF-based materials. In this review, we present a critical overview on the recent progress of the use of MOF-based materials for gaseous fuel storage, chemical hydrogen storage, solar and electrochemical energy storage and conversion. The challenges and opportunities towards advanced energy technologies with the MOF-based materials are discussed.

516 citations


Journal ArticleDOI
09 Jan 2020-Chem
TL;DR: In this article, metal-organic framework (MOF)-derived carbon materials (CMs) have drawn great interest in many fields of application, such as energy storage and conversion, environmental remediation, and catalysis.

476 citations


Journal ArticleDOI
TL;DR: The design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co3O4 nanocube@Co-MOF (Co3O-Co- MOF) is presented, via a controllable and facile one-pot hydrothermal method underhighly alkaline conditions.
Abstract: Most metal-organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to alkaline aqueous solutions, thus precluding their use as potential electrode materials for electrochemical energy storage devices. Here, we present the design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co3O4 nanocube@Co-MOF (Co3O4@Co-MOF), via a controllable and facile one-pot hydrothermal method under highly alkaline conditions. The obtained composite possesses exceptional alkaline stability, retaining its original structure in 3.0 M KOH for at least 15 days. Benefitting from the exceptional alkaline stability, unique structure, and larger surface area, the Co3O4@Co-MOF composite shows a specific capacitance as high as 1020 F g-1 at 0.5 A g-1 and a high cycling stability with only 3.3% decay after 5000 cycles at 5 A g-1. The as-constructed solid-state flexible device exhibits a maximum energy density of 21.6 mWh cm-3.

460 citations



Journal ArticleDOI
Sean Walkowiak1, Sean Walkowiak2, Liangliang Gao3, Cécile Monat4, Georg Haberer, Mulualem T. Kassa5, Jemima Brinton6, Ricardo H. Ramirez-Gonzalez6, Markus C. Kolodziej7, Emily Delorean3, Dinushika Thambugala8, Valentyna Klymiuk1, Brook Byrns1, Heidrun Gundlach, Venkat Bandi1, Jorge Nunez Siri1, Kirby T. Nilsen1, Catharine Aquino, Axel Himmelbach4, Dario Copetti7, Dario Copetti9, Tomohiro Ban10, Luca Venturini11, Michael W. Bevan6, Bernardo J. Clavijo6, Dal-Hoe Koo3, Jennifer Ens1, Krystalee Wiebe1, Amidou N’Diaye1, Allen K. Fritz3, Carl Gutwin1, Anne Fiebig4, Christine Fosker6, Bin Xiao Fu2, Gonzalo Garcia Accinelli6, Keith A. Gardner, Nick Fradgley, Juan J. Gutierrez-Gonzalez12, Gwyneth Halstead-Nussloch7, Masaomi Hatakeyama7, Chu Shin Koh1, Jasline Deek13, Alejandro C. Costamagna14, Pierre R. Fobert5, Darren Heavens6, Hiroyuki Kanamori, Kanako Kawaura10, Fuminori Kobayashi, Ksenia V. Krasileva6, Tony Kuo15, Tony Kuo16, Neil McKenzie6, Kazuki Murata17, Yusuke Nabeka17, Timothy Paape7, Sudharsan Padmarasu4, Lawrence Percival-Alwyn, Sateesh Kagale5, Uwe Scholz4, Jun Sese15, Philomin Juliana18, Ravi P. Singh18, Rie Shimizu-Inatsugi7, David Swarbreck6, James Cockram, Hikmet Budak, Toshiaki Tameshige10, Tsuyoshi Tanaka, Hiroyuki Tsuji10, Jonathan M. Wright6, Jianzhong Wu, Burkhard Steuernagel6, Ian Small19, Sylvie Cloutier8, Gabriel Keeble-Gagnère, Gary J. Muehlbauer12, Josquin Tibbets, Shuhei Nasuda17, Joanna Melonek19, Pierre Hucl1, Andrew G. Sharpe1, Matthew D. Clark11, Erik Legg20, Arvind K. Bharti20, Peter Langridge21, Anthony Hall6, Cristobal Uauy6, Martin Mascher4, Simon G. Krattinger22, Simon G. Krattinger7, Hirokazu Handa23, Kentaro Shimizu10, Kentaro Shimizu7, Assaf Distelfeld24, Kenneth J. Chalmers21, Beat Keller7, Klaus F. X. Mayer25, Jesse Poland3, Nils Stein4, Nils Stein26, Curt A. McCartney8, Manuel Spannagl, Thomas Wicker7, Curtis J. Pozniak1 
25 Nov 2020-Nature
TL;DR: Comparative analysis of multiple genome assemblies from wheat reveals extensive diversity that results from the complex breeding history of wheat and provides a basis for further potential improvements to this important food crop.
Abstract: Advances in genomics have expedited the improvement of several agriculturally important crops but similar efforts in wheat (Triticum spp.) have been more challenging. This is largely owing to the size and complexity of the wheat genome1, and the lack of genome-assembly data for multiple wheat lines2,3. Here we generated ten chromosome pseudomolecule and five scaffold assemblies of hexaploid wheat to explore the genomic diversity among wheat lines from global breeding programs. Comparative analysis revealed extensive structural rearrangements, introgressions from wild relatives and differences in gene content resulting from complex breeding histories aimed at improving adaptation to diverse environments, grain yield and quality, and resistance to stresses4,5. We provide examples outlining the utility of these genomes, including a detailed multi-genome-derived nucleotide-binding leucine-rich repeat protein repertoire involved in disease resistance and the characterization of Sm16, a gene associated with insect resistance. These genome assemblies will provide a basis for functional gene discovery and breeding to deliver the next generation of modern wheat cultivars.

Journal ArticleDOI
15 Jan 2020-Nature
TL;DR: A hypothetical model for eukaryogenesis is proposed, termed the entangle–engulf–endogenize (also known as E 3 ) model, and isolation and characterization of an Asgard archaeon related to Lokiarchaeota reveals insights into how eukARYotes may have evolved from prokaryotes.
Abstract: The origin of eukaryotes remains unclear1–4. Current data suggest that eukaryotes may have emerged from an archaeal lineage known as ‘Asgard’ archaea5,6. Despite the eukaryote-like genomic features that are found in these archaea, the evolutionary transition from archaea to eukaryotes remains unclear, owing to the lack of cultured representatives and corresponding physiological insights. Here we report the decade-long isolation of an Asgard archaeon related to Lokiarchaeota from deep marine sediment. The archaeon—‘Candidatus Prometheoarchaeum syntrophicum’ strain MK-D1—is an anaerobic, extremely slow-growing, small coccus (around 550 nm in diameter) that degrades amino acids through syntrophy. Although eukaryote-like intracellular complexes have been proposed for Asgard archaea6, the isolate has no visible organelle-like structure. Instead, Ca. P. syntrophicum is morphologically complex and has unique protrusions that are long and often branching. On the basis of the available data obtained from cultivation and genomics, and reasoned interpretations of the existing literature, we propose a hypothetical model for eukaryogenesis, termed the entangle–engulf–endogenize (also known as E3) model. Isolation and characterization of an archaeon that is most closely related to eukaryotes reveals insights into how eukaryotes may have evolved from prokaryotes.

Journal ArticleDOI
TL;DR: This review summarizes the different properties of gas hydrates as well as their formation and dissociation kinetics and then reviews the fast-growing literature reporting their role and applications in the aforementioned fields, mainly concentrating on advances during the last decade.
Abstract: Gas hydrates have received considerable attention due to their important role in flow assurance for the oil and gas industry, their extensive natural occurrence on Earth and extraterrestrial planets, and their significant applications in sustainable technologies including but not limited to gas and energy storage, gas separation, and water desalination Given not only their inherent structural flexibility depending on the type of guest gas molecules and formation conditions, but also the synthetic effects of a wide range of chemical additives on their properties, these variabilities could be exploited to optimise the role of gas hydrates This includes increasing their industrial applications, understanding and utilising their role in Nature, identifying potential methods for safely extracting natural gases stored in naturally occurring hydrates within the Earth, and for developing green technologies This review summarizes the different properties of gas hydrates as well as their formation and dissociation kinetics and then reviews the fast-growing literature reporting their role and applications in the aforementioned fields, mainly concentrating on advances during the last decade Challenges, limitations, and future perspectives of each field are briefly discussed The overall objective of this review is to provide readers with an extensive overview of gas hydrates that we hope will stimulate further work on this riveting field

Journal ArticleDOI
TL;DR: MOF was constructed as front surface layer to maintain a supersaturated electrolyte layer on Zn anode and provides a promising approach to realize supersaturated inner layer and safe Zn batteries.
Abstract: Rechargeable aqueous zinc batteries (RAZB) have been re-evaluated because of the superiority in addressing safety and cost concerns. Nonetheless, the limited lifespan arising from dendritic electrodeposition of metallic Zn hinders their further development. Herein, a metal-organic framework (MOF) was constructed as front surface layer to maintain a super-saturated electrolyte layer on the Zn anode. Raman spectroscopy indicated that the highly coordinated ion complexes migrating through the MOF channels were different from the solvation structure in bulk electrolyte. Benefiting from the unique super-saturated front surface, symmetric Zn cells survived up to 3000 hours at 0.5 mA cm-2 , near 55-times that of bare Zn anodes. Moreover, aqueous MnO2 -Zn batteries delivered a reversible capacity of 180.3 mAh g-1 and maintained a high capacity retention of 88.9 % after 600 cycles with MnO2 mass loading up to 4.2 mg cm-2 .

Journal ArticleDOI
TL;DR: In this paper, the state-of-the-art, current and future challenges, as well as the advances in science and technology needed to meet these challenges are presented, along with the state of the art, the current and the future challenges.
Abstract: Plasma catalysis is gaining increasing interest for various gas conversion applications, such as CO2 conversion into value-added chemicals and fuels, CH4 activation into hydrogen, higher hydrocarbons or oxygenates, and NH3 synthesis Other applications are already more established, such as for air pollution control, eg volatile organic compound remediation, particulate matter and NOx removal In addition, plasma is also very promising for catalyst synthesis and treatment Plasma catalysis clearly has benefits over 'conventional' catalysis, as outlined in the Introduction However, a better insight into the underlying physical and chemical processes is crucial This can be obtained by experiments applying diagnostics, studying both the chemical processes at the catalyst surface and the physicochemical mechanisms of plasma-catalyst interactions, as well as by computer modeling The key challenge is to design cost-effective, highly active and stable catalysts tailored to the plasma environment Therefore, insight from thermal catalysis as well as electro- and photocatalysis is crucial All these aspects are covered in this Roadmap paper, written by specialists in their field, presenting the state-of-the-art, the current and future challenges, as well as the advances in science and technology needed to meet these challenges

Journal ArticleDOI
TL;DR: The scope of the advancement in terms of structural and physicochemical attributes and their effects on biomedical applications with a particular focus on recent studies is emphasized.
Abstract: Mesoporous silica nanoparticles (MSNs), one of the important porous materials, have garnered interest owing to their highly attractive physicochemical features and advantageous morphological attributes. They are of particular importance for use in diverse fields including, but not limited to, adsorption, catalysis, and medicine. Despite their intrinsic stable siliceous frameworks, excellent mechanical strength, and optimal morphological attributes, pristine MSNs suffer from poor drug loading efficiency, as well as compatibility and degradability issues for therapeutic, diagnostic, and tissue engineering purposes. Collectively, the desirable and beneficial properties of MSNs have been harnessed by modifying the surface of the siliceous frameworks through incorporating supramolecular assemblies and various metal species, and through incorporating supramolecular assemblies and various metal species and their conjugates. Substantial advancements of these innovative colloidal inorganic nanocontainers drive researchers in promoting them toward innovative applications like stimuli (light/ultrasound/magnetic)-responsive delivery-associated therapies with exceptional performance in vivo. Here, a brief overview of the fabrication of siliceous frameworks, along with discussions on the significant advances in engineering of MSNs, is provided. The scope of the advancement in terms of structural and physicochemical attributes and their effects on biomedical applications with a particular focus on recent studies is emphasized. Finally, interesting perspectives are recapitulated, along with the scope toward clinical translation.

Journal ArticleDOI
TL;DR: In this article, a detailed overview of ammonia as a fuel for compression ignition engines is provided, which can be combusted with diesel or any other lower autoignition temperature fuel in dual-fuel mode and lead to a significant reduction of carbon-based emissions.

Journal ArticleDOI
TL;DR: In this paper, the authors discuss the key roles and the critical issues of single/dual-atom and cluster catalysts, and the great opportunities furnished by metal-organic frameworks for the construction strategy.
Abstract: Single/dual-atom and cluster metal catalysts, with much higher atom-utilization efficiency, remarkable performance, good recyclability and unique properties, have emerged as a new frontier in energy-related catalysis. In recent years, metal–organic frameworks (MOFs) have demonstrated great potential for the targeted creation of single/dual-atom and cluster catalysts, featuring the distinctive advantages of high metal loadings, porous structures and tailorable catalytic sites. In this review, we discuss the key roles and the critical issues of single/dual-atom and cluster catalysts, and the great opportunities furnished by MOFs for the construction strategy. The accessible characterization techniques for single/dual-atom and cluster catalysts will be showcased. Furthermore, we highlight recent advances in the construction and energy applications of MOF-based single/dual-atom and cluster catalysts by taking advantage of structural features of MOFs. Current issues, promising ideas and future prospects for MOF-based single/dual-atom and cluster catalysts are given.

Journal ArticleDOI
TL;DR: A highly active and very stable trifunctional electrocatalyst composed of Co2 P embedded in Co, N, and P multi-doped carbon has been synthesized using zeolitic imidazolate frameworks as precursors, representing a breakthrough in improving the catalytic performance of non-precious metal electrocatalysts for OER, HER, and ORR.
Abstract: Developing efficient and low-cost replacements for precious metals as electrocatalysts active in electrochemical reactions-the oxygen evolution reaction (OER), hydrogen evolution reaction (HER), and oxygen reduction reaction (ORR)-is a top priority in renewable energy technology. In this work a highly active and very stable trifunctional electrocatalyst composed of Co2 P embedded in Co, N, and P multi-doped carbon has been synthesized using zeolitic imidazolate frameworks as precursors. The synergistic effects between Co2 P and the multi-heteroatom-doped carbon substrates afford materials having electrocatalytic activities for HER, OER, and ORR, which are comparable-or even superior to-those of commercial RuO2 or Pt/C catalysts. Density functional theory calculations show that Co2 P has a higher density of states at the Fermi level than Con P (0 < n < 2), which promotes electron transfer and intermediates adsorption in the catalytic process. Zinc-air batteries and water splitting devices assembled using the materials as electrode electrocatalysts show good performance and outstanding stability. This work represents a breakthrough in improving the catalytic performance of non-precious metal electrocatalysts for OER, HER, and ORR, and opens new avenues for clean energy generation.

Journal ArticleDOI
TL;DR: This work systematically explore the phylogeny of taxa currently assigned to these classes using 120 conserved single-copy marker genes as well as rRNA genes and indicates the independent acquisition of predatory behaviour in the phyla Myxococcota and Bdellovibrio, which is consistent with their distinct modes of action.
Abstract: The class Deltaproteobacteria comprises an ecologically and metabolically diverse group of bacteria best known for dissimilatory sulphate reduction and predatory behaviour. Although this lineage is the fourth described class of the phylum Proteobacteria, it rarely affiliates with other proteobacterial classes and is frequently not recovered as a monophyletic unit in phylogenetic analyses. Indeed, one branch of the class Deltaproteobacteria encompassing Bdellovibrio-like predators was recently reclassified into a separate proteobacterial class, the Oligoflexia. Here we systematically explore the phylogeny of taxa currently assigned to these classes using 120 conserved single-copy marker genes as well as rRNA genes. The overwhelming majority of markers reject the inclusion of the classes Deltaproteobacteria and Oligoflexia in the phylum Proteobacteria. Instead, the great majority of currently recognized members of the class Deltaproteobacteria are better classified into four novel phylum-level lineages. We propose the names Desulfobacterota phyl. nov. and Myxococcota phyl. nov. for two of these phyla, based on the oldest validly published names in each lineage, and retain the placeholder name SAR324 for the third phylum pending formal description of type material. Members of the class Oligoflexia represent a separate phylum for which we propose the name Bdellovibrionota phyl. nov. based on priority in the literature and general recognition of the genus Bdellovibrio. Desulfobacterota phyl. nov. includes the taxa previously classified in the phylum Thermodesulfobacteria, and these reclassifications imply that the ability of sulphate reduction was vertically inherited in the Thermodesulfobacteria rather than laterally acquired as previously inferred. Our analysis also indicates the independent acquisition of predatory behaviour in the phyla Myxococcota and Bdellovibrionota, which is consistent with their distinct modes of action. This work represents a stable reclassification of one of the most taxonomically challenging areas of the bacterial tree and provides a robust framework for future ecological and systematic studies.

Journal ArticleDOI
TL;DR: This catalyst demonstrates superior ORR performances in both alkaline and acidic electrolytes, comparable to the state-of-the-art Pt/C catalyst and superior to most of the precious-metal-free catalysts reported to date.
Abstract: Single-atom catalysts have drawn great attention, especially in electrocatalysis. However, most of previous works focus on the enhanced catalytic properties via improving metal loading. Engineering morphologies of catalysts to facilitate mass transport through catalyst layers, thus increasing the utilization of each active site, is regarded as an appealing way for enhanced performance. Herein, we design an overhang-eave structure decorated with isolated single-atom iron sites via a silica-mediated MOF-templated approach for oxygen reduction reaction (ORR) catalysis. This catalyst demonstrates superior ORR performance in both alkaline and acidic electrolytes, comparable to the state-of-the-art Pt/C catalyst and superior to most precious-metal-free catalysts reported to date. This activity originates from its edge-rich structure, having more three-phase boundaries with enhanced mass transport of reactants to accessible single-atom iron sites (increasing the utilization of active sites), which verifies the practicability of such a synthetic approach.

Journal ArticleDOI
TL;DR: Bimetallic MOF derivatives show exposed active sites, good stability and conductivity, enabling them to extend their applications to the catalysis of more challenging reactions and electrochemical energy storage and conversion.
Abstract: Bimetallic metal-organic frameworks (MOFs) have two different metal ions in the inorganic nodes. According to the metal distribution, the architecture of bimetallic MOFs can be classified into two main categories namely solid solution and core-shell structures. Various strategies have been developed to prepare bimetallic MOFs with controlled compositions and structures. Bimetallic MOFs show a synergistic effect and enhanced properties compared to their monometallic counterparts and have found many applications in the fields of gas adsorption, catalysis, energy storage and conversion, and luminescence sensing. Moreover, bimetallic MOFs can serve as excellent precursors/templates for the synthesis of functional nanomaterials with controlled sizes, compositions, and structures. Bimetallic MOF derivatives show exposed active sites, good stability and conductivity, enabling them to extend their applications to the catalysis of more challenging reactions and electrochemical energy storage and conversion. This review provides an overview of the significant advances in the development of bimetallic MOFs and their derivatives with special emphases on their preparation and applications.

Journal ArticleDOI
TL;DR: Liu et al. as mentioned in this paper employed a holistic interface stabilization strategy by modifying all the relevant layers and interfaces, namely the perovskite layer, charge transporting layers and device encapsulation.
Abstract: The upscaling of perovskite solar cells to module scale and long-term stability have been recognized as the most important challenges for the commercialization of this emerging photovoltaic technology. In a perovskite solar module, each interface within the device contributes to the efficiency and stability of the module. Here, we employed a holistic interface stabilization strategy by modifying all the relevant layers and interfaces, namely the perovskite layer, charge transporting layers and device encapsulation, to improve the efficiency and stability of perovskite solar modules. The treatments were selected for their compatibility with low-temperature scalable processing and the module scribing steps. Our unencapsulated perovskite solar modules achieved a reverse-scan efficiency of 16.6% for a designated area of 22.4 cm2. The encapsulated perovskite solar modules, which show efficiencies similar to the unencapsulated one, retained approximately 86% of the initial performance after continuous operation for 2,000 h under AM1.5G light illumination, which translates into a T90 lifetime (the time over which the device efficiency reduces to 90% of its initial value) of 1,570 h and an estimated T80 lifetime (the time over which the device efficiency reduces to 80% of its initial value) of 2,680 h. The upscaling of layer treatments and processing that afford high efficiency and stability in small-area perovskite solar cells remains challenging. Liu et al. show how the efficiency and stability of perovskite modules can be improved using an integrated approach to interface and layer engineering.

Journal ArticleDOI
TL;DR: The latest research progress in catalytic hydrogen production is summarized, by using metal nanocatalysts confined within diverse nanoporous materials, such as metal-organic frameworks, porous carbons, zeolites, mesoporous silica, and porous organic polymers.
Abstract: Hydrogen has emerged as an environmentally attractive fuel and a promising energy carrier for future applications to meet the ever-increasing energy challenges. The safe and efficient storage and release of hydrogen remain a bottleneck for realizing the upcoming hydrogen economy. Hydrogen storage based on liquid-phase chemical hydrogen storage materials is one of the most promising hydrogen storage techniques, which offers considerable potential for large-scale practical applications for its excellent safety, great convenience, and high efficiency. Recently, nanopore-supported metal nanocatalysts have stood out remarkably in boosting the field of liquid-phase chemical hydrogen storage. Herein, the latest research progress in catalytic hydrogen production is summarized, from liquid-phase chemical hydrogen storage materials, such as formic acid, ammonia borane, hydrous hydrazine, and sodium borohydride, by using metal nanocatalysts confined within diverse nanoporous materials, such as metal-organic frameworks, porous carbons, zeolites, mesoporous silica, and porous organic polymers. The state-of-the-art synthetic strategies and advanced characterizations for these nanocatalysts, as well as their catalytic performances in hydrogen generation, are presented. The limitation of each hydrogen storage system and future challenges and opportunities on this subject are also discussed. References in related fields are provided, and more developments and applications to achieve hydrogen energy will be inspired.

Journal ArticleDOI
08 Jan 2020-Nature
TL;DR: The synthesis of surprisingly stable, free-standing single layers of amorphous carbon and their analysis by atomic-resolution imaging could settle a debate about their atomic arrangement and offer unusual electronics applications.
Abstract: Bulk amorphous materials have been studied extensively and are widely used, yet their atomic arrangement remains an open issue. Although they are generally believed to be Zachariasen continuous random networks1, recent experimental evidence favours the competing crystallite model in the case of amorphous silicon2–4. In two-dimensional materials, however, the corresponding questions remain unanswered. Here we report the synthesis, by laser-assisted chemical vapour deposition5, of centimetre-scale, free-standing, continuous and stable monolayer amorphous carbon, topologically distinct from disordered graphene. Unlike in bulk materials, the structure of monolayer amorphous carbon can be determined by atomic-resolution imaging. Extensive characterization by Raman and X-ray spectroscopy and transmission electron microscopy reveals the complete absence of long-range periodicity and a threefold-coordinated structure with a wide distribution of bond lengths, bond angles, and five-, six-, seven- and eight-member rings. The ring distribution is not a Zachariasen continuous random network, but resembles the competing (nano)crystallite model6. We construct a corresponding model that enables density-functional-theory calculations of the properties of monolayer amorphous carbon, in accordance with observations. Direct measurements confirm that it is insulating, with resistivity values similar to those of boron nitride grown by chemical vapour deposition. Free-standing monolayer amorphous carbon is surprisingly stable and deforms to a high breaking strength, without crack propagation from the point of fracture. The excellent physical properties of this stable, free-standing monolayer amorphous carbon could prove useful for permeation and diffusion barriers in applications such as magnetic recording devices and flexible electronics. The synthesis of surprisingly stable, free-standing single layers of amorphous carbon and their analysis by atomic-resolution imaging could settle a debate about their atomic arrangement and offer unusual electronics applications.

Journal ArticleDOI
TL;DR: In this article, a few-layer bismuthene (Bi-ene) was obtained by an in-situ electrochemical transformation from ultrathin bismuth-based metal-organic layers.
Abstract: Electrochemical reduction of CO2 to valuable fuels is appealing for CO2 fixation and energy storage. However, the development of electrocatalysts with high activity and selectivity in a wide potential window is challenging. Herein, atomically thin bismuthene (Bi-ene) is pioneeringly obtained by an in situ electrochemical transformation from ultrathin bismuth-based metal-organic layers. The few-layer Bi-ene, which possesses a great mass of exposed active sites with high intrinsic activity, has a high selectivity (ca. 100 %), large partial current density, and quite good stability in a potential window exceeding 0.35 V toward formate production. It even deliver current densities that exceed 300.0 mA cm-2 without compromising selectivity in a flow-cell reactor. Using in situ ATR-IR spectra and DFT analysis, a reaction mechanism involving HCO3- for formate generation was unveiled, which brings new fundamental understanding of CO2 reduction.

Journal ArticleDOI
03 Apr 2020-Science
TL;DR: An impact experiment on Ryugu is described using Hayabusa2’s Small Carry-on Impactor, which produced an artificial crater with a diameter >10 meters, which has a semicircular shape, an elevated rim, and a central pit, and implications for Ryugu's surface age are discussed.
Abstract: The Hayabusa2 spacecraft investigated the small asteroid Ryugu, which has a rubble-pile structure. We describe an impact experiment on Ryugu using Hayabusa2's Small Carry-on Impactor. The impact produced an artificial crater with a diameter >10 meters, which has a semicircular shape, an elevated rim, and a central pit. Images of the impact and resulting ejecta were recorded by the Deployable CAMera 3 for >8 minutes, showing the growth of an ejecta curtain (the outer edge of the ejecta) and deposition of ejecta onto the surface. The ejecta curtain was asymmetric and heterogeneous and it never fully detached from the surface. The crater formed in the gravity-dominated regime; in other words, crater growth was limited by gravity not surface strength. We discuss implications for Ryugu's surface age.

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31 Jan 2020-Science
TL;DR: In this article, the experimental synthesis of one-dimensional van der Waals heterostructures, a class of materials where different atomic layers are coaxially stacked, was presented, and the growth of single-crystal layers of hexagonal boron nitride (BN) and molybdenum disulfide (MoS2) crystals on singlewalled carbon nanotubes (SWCNTs) was demonstrated.
Abstract: We present the experimental synthesis of one-dimensional (1D) van der Waals heterostructures, a class of materials where different atomic layers are coaxially stacked. We demonstrate the growth of single-crystal layers of hexagonal boron nitride (BN) and molybdenum disulfide (MoS2) crystals on single-walled carbon nanotubes (SWCNTs). For the latter, larger-diameter nanotubes that overcome strain effect were more readily synthesized. We also report a 5-nanometer-diameter heterostructure consisting of an inner SWCNT, a middle three-layer BN nanotube, and an outer MoS2 nanotube. Electron diffraction verifies that all shells in the heterostructures are single crystals. This work suggests that all of the materials in the current 2D library could be rolled into their 1D counterparts and a plethora of function-designable 1D heterostructures could be realized.

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TL;DR: A review of established laser‐based methodologies of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non‐equilibrium compounds, metal‐oxide core–shells and other anisotropic morphologies is presented.
Abstract: Although oxide nanoparticles are ubiquitous in science and technology, a multitude of compositions, phases, structures, and doping levels exist, each one requiring a variety of conditions for their synthesis and modification. Besides, experimental procedures are frequently dominated by high temperatures or pressures and by chemical contaminants or waste. In recent years, laser synthesis of colloids emerged as a versatile approach to access a library of clean oxide nanoparticles relying on only four main strategies running at room temperature and ambient pressure: laser ablation in liquid, laser fragmentation in liquid, laser melting in liquid and laser defect-engineering in liquid. Here, established laser-based methodologies are reviewed through the presentation of a panorama of oxide nanoparticles which include pure oxidic phases, as well as unconventional structures like defective or doped oxides, non-equilibrium compounds, metal-oxide core-shells and other anisotropic morphologies. So far, these materials showed several useful properties that are discussed with special emphasis on catalytic, biomedical and optical application. Yet, given the endless number of mixed compounds accessible by the laser-assisted methodologies, there is still a lot of room to expand the library of nano-crystals and to refine the control over products as well as to improve the understanding of the whole process of nanoparticle formation. To that end, this review aims to identify the perspectives and unique opportunities of laser-based synthesis and processing of colloids for future studies of oxide nanomaterial-oriented sciences.