Remnant Copper Cation-Assisted Atom Mixing in Multicomponent Nanoparticles.

Nanostructured high-/medium-entropy compounds have emerged as important catalytic materials for energy conversion technologies, but complex thermodynamic relationships involved with the element mixing enthalpy have been a considerable roadblock to the formation of stable single-phase structures. Cation exchange reactions (CERs), in particular with copper sulfide templates, have been extensively investigated for the synthesis of multicomponent heteronanoparticles with unconventional structural features. Because copper cations within the host copper sulfide templates are stoichiometrically released with incoming foreign cations in CERs to maintain the overall charge balance, the complete absence of Cu cations in the nanocrystals after initial CERs would mean that further compositional variation would not be possible by subsequent CERs. Herin, we successfully retained a portion of Cu cations within the silver sulfide (Ag2S) and gold sulfide (Au2S) phases of Janus Cu2-xS-M2S (M = Ag, Au) nanocrystals after the CERs, by partially suppressing the transformation of the anion sublattice that inevitably occurs during the introduction of external cations. Interestingly, the subsequent CERs on Janus Cu1.81S-M2S (M = Ag, Au), by utilizing the remnant Cu cations, allowed the construction of Janus Cu1.81S-AgxAuyS, which preserved the initial heterointerface. The synthetic strategy described in this work to suppress the complete removal of the Cu cation from the template could fabricate the CER-driven heterostructures with greatly diversified compositions, which exhibit unusual optical and catalytic properties.

Nanoscale-Confined Synthesis of 2D Metal Compounds for Electrochemical Applications.

2D metal compounds, such as transition metal dichalcogenides (TMDs), layered double hydroxides (LDHs), and MXenes, are emerging as important electrocatalyst materials in the transition to a sustainable energy future. Aided by their high surface area, electrical conductivity, and tunable electronic properties, these materials have provided a crucial research thrust in enhancing the efficiency of green hydrogen production, fuel cells, and carbon reduction processes. Most importantly, the synthesis of nanostructured 2D compounds, while challenging, is the key to optimizing their catalytic performance. Recent advancements in this field have highlighted the potential of 2D metal compounds in revolutionizing energy conversion technologies, which entails the discovery of new material compositions, the development of novel synthetic routes, and the integration of these materials into practical energy conversion systems. This review presents an overview of the distinctive characteristics of nanoscale-confined 2D metal compounds, the challenges encountered in their synthesis, and electrochemical applications.

Strategies to Modulate the Copper Oxidation State Toward Selective C2+ Production in the Electrochemical CO2 Reduction Reaction.

The electrochemical reduction of CO2 to form value-added chemicals receives considerable attention in recent years. Copper (Cu) is recognized as the only element capable of electro-reducing CO2 into hydrocarbons with two or more carbon atoms (C2+), but the low product selectivity of the Cu-based catalyst remains a major technological challenge to overcome. Therefore, identification of the structural features of Cu-based catalysts is of great importance for the highly selective production of C2+ products (ethylene, ethanol, n-propanol, etc.), and the oxidation state of Cu species in the catalysts is found critical to the catalyst performance. This review introduces recent efforts to fine-tune the oxidation state of Cu to increase carbon capture and produce specific C2+ compounds, with the intention of greatly expediting the advance in the catalyst designs. It also points to the remaining challenges and fruitful research directions for the development of Cu-based catalysts that can shape the practical CO2 reduction technology.

Three-dimensional reconstruction of Y-IrNi rhombic dodecahedron nanoframe by STEM/EDS tomography.

The structural analysis of nanocrystals via transmission electron microscopy (TEM) is a valuable technique for the material science field. Recently, two-dimensional images by scanning TEM (STEM) and energy-dispersive X-ray spectroscopy (EDS) have successfully extended to three-dimensional (3D) imaging by tomography. However, despite improving TEM instruments and measurement techniques, detector shadowing, the missing-wedge problem, X-ray absorption effects, etc., significant challenges still remain; therefore, the various required corrections should be considered and applied when performing quantitative tomography. Nonetheless, this 3D reconstruction technique can facilitate active site analysis and the development of nanocatalyst systems, such as water electrolysis and fuel cell. Herein, we present a 3D reconstruction technique to obtain tomograms of IrNi rhombic dodecahedral nanoframes (IrNi-RFs) from STEM and EDS images by applying simultaneous iterative reconstruction technique and total variation minimization algorithms. From characterizing the morphology and spatial chemical composition of the Ir and Ni atoms in the nanoframes, we were able to infer the origin of the physical and catalytic durability of IrNi-RFs. Also, by calculating the surface area and volume of the 3D reconstructed model, we were able to quantify the Ir-to-Ni composition ratio and compare it to the EDS measurement result.

Performance Promotion of Multipurpose Catalysts Using Increased Oxygen Vacancy Amounts by Charge-Mismatched Doping.

Modulating the oxygen vacancy (V0) in nanostructures has opened a new avenue for efficient catalyst design, facilitating biomass oxidation reactions and electrocatalytic properties. In this study, we have investigated the properties of NiO-based catalysts with varying degrees of V0 achieved through ion doping of the catalyst with cations of different oxidation states (TM3+) or the same valence state (TM2+) as Ni2+ in the NiO matrix. By introducing charge-mismatched dopants, we enhanced the concentration of V0 in the NiO catalyst, resulting in remarkable selectivity (∼50%) for the conversion of 2,5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), as well as a lower overpotential in the oxygen evolution reaction (OER). We believe that charge-mismatched doping offers a novel avenue for optimizing defect engineering in oxide-based catalysts, which can enable more efficient biomass conversion and water splitting. These findings have made a significant contribution to the field of multipurpose catalysis and hold the potential to inspire new catalyst designs that would usher in a more sustainable future.

Electrochemically Activatable Liquid Organic Hydrogen Carriers and Their Applications.

Hydrogen has been chosen as an environmentally benign energy source to replace fossil-fuel-based energy systems. Since hydrogen is difficult to store and transport in its gaseous phase, thermochemical liquid organic hydrogen carriers (LOHCs) have been developed as one of the alternative technologies. However, the high temperature and pressure requirements of thermochemical LOHC systems result in huge energy waste and impracticality. This Perspective proposes electrochemical (EC)-LOHCs capable of more efficient, safer, and lower temperature and pressure hydrogen storage/utilization. To enable this technology, several EC-LOHC candidates such as isopropanol, phenolic compounds, and organic acids are described, and the latest research trends and design concepts of related homo/hetero-based electrocatalysts are discussed. In addition, we propose efficient fuel-cell-based systems that implement electrochemical (de)hydrogenation of EC-LOHCs and present prospects for relevant technologies.

Perovskite Nanocrystals Protected by Hermetically Sealing for Highly Bright and Stable Deep-Blue Light-Emitting Diodes.

Metal-halide perovskite nanocrystals (NCs) have emerged as suitable light-emitting materials for light-emitting diodes (LEDs) and other practical applications. However, LEDs with perovskite NCs undergo environment-induced and ion-migration-induced structural degradation during operation; therefore, novel NC design concepts, such as hermetic sealing of the perovskite NCs, are required. Thus far, viable synthetic conditions to form a robust and hermetic semiconducting shell on perovskite NCs have been rarely reported for LED applications because of the difficulties in the delicate engineering of encapsulation techniques. Herein, a highly bright and durable deep-blue perovskite LED (PeLED) formed by hermetically sealing perovskite NCs with epitaxial ZnS shells is reported. This shell protects the perovskite NCs from the environment, facilitates charge injection/transport, and effectively suppresses interparticle ion migration during the LED operation, resulting in exceptional brightness (2916 cd m-2 ) at 451 nm and a high external quantum efficiency of 1.32%. Furthermore, even in the unencapsulated state, the LED shows a long operational lifetime (T50 ) of 1192 s (≈20 min) in the air. These results demonstrate that the epitaxial and hermetic encapsulation of perovskite NCs is a powerful strategy for fabricating high-performance deep-blue-emitting PeLEDs.

Electrochemical Nitrogen Fixation for Green Ammonia: Recent Progress and Challenges.

Ammonia, a key feedstock used in various industries, has been considered a sustainable fuel and energy storage option. However, NH3 production via the conventional Haber-Bosch process is costly, energy-intensive, and significantly contributing to a massive carbon footprint. An electrochemical synthetic pathway for nitrogen fixation has recently gained considerable attention as NH3 can be produced through a green process without generating harmful pollutants. This review discusses the recent progress and challenges associated with the two relevant electrochemical pathways: direct and indirect nitrogen reduction reactions. The detailed mechanisms of these reactions and highlight the recent efforts to improve the catalytic performances are discussed. Finally, various promising research strategies and remaining tasks are presented to highlight future opportunities in the electrochemical nitrogen reduction reaction.

Intermetallic Nanoarchitectures for Efficient Electrocatalysis.

Intermetallic structures whose regular atomic arrays of constituent elements present unique catalytic properties have attracted considerable attention as efficient electrocatalysts for energy conversion reactions. Further performance enhancement in intermetallic catalysts hinges on constructing catalytic surfaces possessing high activity, durability, and selectivity. In this Perspective, we introduce recent endeavors to boost the performance of intermetallic catalysts by generating nanoarchitectures, which have well-defined size, shape, and dimension. We discuss the beneficial effects of nanoarchitectures compared with simple nanoparticles in catalysis. We highlight that the nanoarchitectures have high intrinsic activity owing to their inherent structural factors, including controlled facets, surface defects, strained surfaces, nanoscale confinement effects, and a high density of active sites. We next present notable examples of intermetallic nanoarchitectures, namely, facet-controlled intermetallic nanocrystals and multidimensional nanomaterials. Finally, we suggest the future research directions of intermetallic nanoarchitectures.

Ultra-Stable and Highly Efficient White Light Emitting Diodes through CsPbBr3 Perovskite Nanocrystals-Silica Composite Phosphor Functionalized with Surface Phenyl Molecules.

Poor stability of CsPbBr3 perovskite nanocrystals (NCs) to moisture/heat/light has significantly limited their application as a green phosphor, despite their outstanding luminescent properties. Here, a remarkably stable CsPbBr3 NCs-silica composite phosphor functionalized with surface phenyl molecules (CsPbBr3 -SiO2 Ph ) is synthesized by controlling low-temperature hydrolysis and condensation reaction of perhydropolysilazane in the presence of CsPbBr3 NCs followed by phenyl-functionalization. Through the process, CsPbBr3 NCs are confined in a compact silica matrix, which is impermeable to H2 O. The synthesis strategy is extended to a classical red quantum dot, CdZnSeS@ZnS NCs, to fabricate a white light emitting diode (WLED) consisting of CsPbBr3 -SiO2 Ph and CdZnSeS@ZnS-SiO2 Ph phosphor and silicone resin packaged on a commercial blue InGaN chip with luminous efficacy (LE) of 9.36 lm W-1 . The WLED undergoes enhancements in both green and red photoluminescence over time to achieve a highly efficient performance of 38.80 lm W-1 . More importantly, the WLED exhibits unprecedented operational stability of LE/LE0  = 94% after 101 h-operation at 20 mA (2.56 V). The ultra-high operational stability and efficient performance are mainly attributed to thermal curing and aging through which grain growth occurs as well as deactivation of defect states by permeated atmospheric O2 .

SegPC-2021: A challenge & dataset on segmentation of Multiple Myeloma plasma cells from microscopic images.

Multiple Myeloma (MM) is an emerging ailment of global concern. Its diagnosis at the early stages is critical for recovery. Therefore, efforts are underway to produce digital pathology tools with human-level intelligence that are efficient, scalable, accessible, and cost-effective. Following the trend, a medical imaging challenge on "Segmentation of Multiple Myeloma Plasma Cells in Microscopic Images (SegPC-2021)" was organized at the IEEE International Symposium on Biomedical Imaging (ISBI), 2021, France. The challenge addressed the problem of cell segmentation in microscopic images captured from the slides prepared from the bone marrow aspirate of patients diagnosed with Multiple Myeloma. The challenge released a total of 775 images with 690 and 85 images of sizes 2040×1536 and 1920×2560 pixels, respectively, captured from two different (microscope and camera) setups. The participants had to segment the plasma cells with a separate label on each cell's nucleus and cytoplasm. This problem comprises many challenges, including a reduced color contrast between the cytoplasm and the background, and the clustering of cells with a feeble boundary separation of individual cells. To our knowledge, the SegPC-2021 challenge dataset is the largest publicly available annotated data on plasma cell segmentation in MM so far. The challenge targets a semi-automated tool to ensure the supervision of medical experts. It was conducted for a span of five months, from November 2020 to April 2021. Initially, the data was shared with 696 people from 52 teams, of which 41 teams submitted the results of their models on the evaluation portal in the validation phase. Similarly, 20 teams qualified for the last round, of which 16 teams submitted the results in the final test phase. All the top-5 teams employed DL-based approaches, and the best mIoU obtained on the final test set of 277 microscopic images was 0.9389. All these five models have been analyzed and discussed in detail. This challenge task is a step towards the target of creating an automated MM diagnostic tool.

Polymer-Covered Copper Catalysts Alter the Reaction Pathway of the Electrochemical CO2 Reduction Reaction.

The electrochemical CO2 reduction reaction (CO2RR) has attracted considerable attention recently due to the potential conversion of atmospheric CO2 into useful organic products by utilizing electricity from renewable energy sources. However, the selective formation of desired products only via CO2RR has been elusive due to the presence of a myriad of competing reaction pathways, thus calling for effective strategies controlling the reaction coordinates. The control of binding energies of the reaction intermediate, such as *CO, is pivotal to manipulating reaction pathways, and various attempts have been made to accomplish this goal. Herein, we introduce recent endeavors to increase the catalytic selectivity of Cu-based catalysts by surface modification with polymer coating, which can change the local pH, hydrophilicity/hydrophobicity, reaction concentration, etc. The polymer conjugation also contributed to the enhanced electrocatalytic stability of Cu-based catalysts during the CO2RR. We also point to the remaining challenges and provide perspectives on the further development of Cu-polymer hybrid catalysts for the practical CO2RR.

Chemical Fields: Directing Atom Migration in the Multiphasic Nanocrystal.

ConspectusAtoms in a bulk solid phase are usually trapped to fixed positions and can change their position only under certain conditions (e.g., at a melting point) due to the high energy barrier of migration between positions within the crystal lattice. Contrary to the atoms in the bulk solid phase, however, atoms in nanoparticles can migrate and change their local positions rather easily, enabled by the high surface energies. The energy states of surface atoms of nanoparticles can be altered by surface-binding moieties, which in turn influence the intrananoparticle migration of atoms at the subsurface of nanoparticles. In 2008, this possibility of intrananoparticle migration was demonstrated with RhPd alloy nanoparticles under the different gas environments of reductive CO or oxidative NO. We envisaged that the explosive expansion of well-defined, multiphasic nanoparticle libraries might be realized by specifically dictating the atom migration direction, by modulating the energy state of specific atoms in the multiphasic nanocrystals. The nanoparticle surface energy is a function of a myriad of factors, namely, surface binding moiety, structural features affecting coordination number of atoms such as nanoparticle geometry, steps, and kinks, and the existence of heterointerface with lattice mismatch. Therefore, all these factors affecting atom energy state in the nanoparticle, categorically termed as "chemical field" (CF), can serve as the driving force for purposeful directional movement of atoms within nanoparticles and subsequent reaction. Geometrically well-defined multiphasic nanocrystals present great promises toward various applications with special emphasis on catalysis and thus are worthy synthetic targets. In recent years, we have demonstrated that manipulation of CFs is an effective synthetic strategy for a variety of geometrically well-defined multiphasic nanocrystals. Herein, we classified multiphasic nanocrystals into metallic alloy systems and ionic systems (metal compounds) because the modes of CF are rather different between these two systems. The migration-directing CFs for neutral metallic atoms are mostly based on the local distribution of elements, degree of alloying, or highly energetic structural features. On the other hand, for the ionic system, structural parameters originating from the discrepancy between cations and anions should be more considered; ionic radii, phase stability, lattice strain, anionic frameworks, cation vacancies, etc. can react as CFs affecting atom migration behavior in the multiphasic ionic nanocrystals. We expect that the limits and potentials of CF-based synthesis of multiphasic nanocrystals described in this work will open a wide avenue to diverse material compositions and geometries, which have been difficult or impossible to approach via conventional nanoparticle synthesis schemes.

Microfluidics-Assisted Synthesis of Hierarchical Cu2 O Nanocrystal as C2 -Selective CO2 Reduction Electrocatalyst.

Copper-based catalysts have attracted enormous attention due to their high selectivity for C2+ products during the electrochemical reduction of CO2 (CO2 RR). In particular, grain boundaries on the catalysts contribute to the generation of various Cu coordination environments, which have been found essential for C-C coupling. However, smooth-surfaced Cu2 O nanocrystals generally lack the ability for the surface reorganization to form multiple grain boundaries and desired Cu undercoordination sites. Flow chemistry armed with the unparalleled ability to mix reaction mixture can achieve a very high concentration of unstable reaction intermediates, which in turn are used up rapidly to lead to kinetics-driven nanocrystal growth. Herein, the synthesis of a unique hierarchical structure of Cu2 O with numerous steps (h-Cu2 O ONS) via flow chemistry-assisted modulation of nanocrystal growth kinetics is reported. The surface of h-Cu2 O ONS underwent rapid surface reconstruction under CO2 RR conditions to exhibit multiple heterointerfaces between Cu2 O and Cu phases, setting the preferable condition to facilitate C-C bond formation. Notably, the h-Cu2 O ONS obtained the increased C2 H4 Faradaic efficiency from 31.9% to 43.5% during electrocatalysis concurrent with the morphological reorganization, showing the role of the stepped surface. Also, the h-Cu2 O ONS demonstrated a 3.8-fold higher ethylene production rate as compared to the Cu2 O nanocube.

Modulating the Local Coordination Environment of Single-Atom Catalysts for Enhanced Catalytic Performance in Hydrogen/Oxygen Evolution Reaction.

Single-atom catalysts (SACs) hold the promise of utilizing 100% of the participating atoms in a reaction as active catalytic sites, achieving a remarkable boost in catalytic efficiency. Thus, they present great potential for noble metal-based electrochemical application systems, such as water electrolyzers and fuel cells. However, their practical applications are severely hindered by intrinsic complications, namely atom agglomeration and relocation, originating from the uncontrollably high surface energy of isolated single-atoms (SAs) during postsynthetic treatment processes or catalytic reactions. Extensive efforts have been made to develop new methodologies for strengthening the interactions between SAs and supports, which could ensure the desired stability of the active catalytic sites and their full utilization by SACs. This review covers the recent progress in SACs development while emphasizing the association between the regulation of coordination environments (e.g., coordination atoms, numbers, sites, structures) and the electrocatalytic performance of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). The crucial role of coordination chemistry in modifying the intrinsic properties of SACs and manipulating their metal-loading, stability, and catalytic properties is elucidated. Finally, the future challenges of SACS development and the industrial outlook of this field are discussed.

Mn-Dopant Differentiating the Ru and Ir Oxidation States in Catalytic Oxides Toward Durable Oxygen Evolution Reaction in Acidic Electrolyte.

Designing an efficient and durable electrocatalyst for the sluggish oxygen evolution reaction (OER) at the anode remains the foremost challenge in developing proton exchange membrane (PEM) electrolyzers. Here, a highly active and durable cactus-like nanoparticle with an exposed heterointerface between the IrO2 and the low oxidation state Ru by introducing a trace amount of Mn dopant is reported. The heterostructure fabrication relies on initial mixing of the Ru and Ir phases before electrochemical oxidation to produce a conjoined Ru/IrO2 heterointerface. Benefitting from electron transfer at the heterointerface, the low oxidation state Ru species shows excellent initial activity, which is maintained even after 180 h of continuous OER test. In a half-cell test, the Mn-doped RuIr nanocactus (Mn-RuIr NCT) achieves a mass activity of 1.85 A mgIr+Ru -1 at 1.48 VRHE , which is 139-fold higher than that of commercial IrO2 . Moreover, the superior electrocatalytic performance of Mn-RuIr NCT in the PEM electrolysis system ensures its viability in practical uses. The results of the excellent catalytic performance for acidic OER indicate that the heterostructuring robust rutile IrO2 and the highly active Ru species with a low oxidation state on the catalyst surface drive a synergistic effect.

Pd3 Pb Nanosponges for Selective Conversion of Furfural to Furfuryl Alcohol under Mild Condition.

Alloy structures with high catalytic surface areas and tunable surface energies can lead to high catalytic selectivity and activities. Herein, the synthesis of sponge-like Pd3 Pb multiframes (Pd3 Pb MFs) is reported by using the thermodynamically driven phase segregation, which exhibit high selectivity (93%) for the conversion of furfural to furfuryl alcohol (FOL) under mild conditions. The excellent catalytic performance of the Pd3 Pb MF catalysts is attributed to the high surface area and optimized surface energy of the catalyst, which is associated with the introduction of Pb to Pd. Density functional theory calculations show that the binding energy of FOL to the surface energy-tuned Pd3 Pb MF is sufficiently lowered to prevent side reactions such as over-hydrogenation of FOL.

Facile one-step synthesis of Ru doped NiCoP nanoparticles as highly efficient electrocatalysts for oxygen evolution reaction.

Transition metal phosphides (TMPs) as ever-evolving electrocatalytic materials have attracted increasing attention in water splitting reactions owing to their cost-effective, highly active and stable catalytic properties. This work presents a facile synthetic route to NiCoP nanoparticles with Ru dopants which function as highly efficient electrocatalysts for oxygen evolution reaction (OER) in alkaline media. The Ru dopants induced a high content of Ni and Co vacancies in NiCoP nanoparticles, and the more defective Ru doped NiCoP phase than undoped NiCoP ones led to a greater number of catalytically active sites and improved electrical conductivity after undergoing electrochemical activation. The Ru doped NiCoP catalyst exhibited high OER catalytic performance in alkaline media with a low overpotential of 281 mV at 10 mA cm-2 and a Tafel slope of 42.7 mV dec-1 .

Directing transition metal-based oxygen-functionalization catalysis.

This review presents the recent progress of oxygen functionalization reactions based on non-electrochemical (conventional organic synthesis) and electrochemical methods. Although both methods have their advantages and limitations, the former approach has been used to synthesize a broader range of organic substances as the latter is limited by several factors, such as poor selectivity and high energy cost. However, because electrochemical methods can replace harmful terminal oxidizers with external voltage, organic electrosynthesis has emerged as greener and more eco-friendly compared to conventional organic synthesis. The progress of electrochemical methods toward oxygen functionalization is presented by an in-depth discussion of different types of electrically driven-chemical organic synthesis, with particular attention to recently developed electrochemical systems and catalyst designs. We hope to direct the attention of readers to the latest breakthroughs of traditional oxygen functionalization reactions and to the potential of electrochemistry for the transformation of organic substrates to useful end products.

Intermetallic PtCu Nanoframes as Efficient Oxygen Reduction Electrocatalysts.

Nanoframe alloy structures represent a class of high-performance catalysts for the oxygen reduction reaction (ORR), owing to their high active surface area, efficient molecular accessibility, and nanoconfinement effect. However, structural and chemical instabilities of nanoframes remain an important challenge. Here, we report the synthesis of PtCu nanoframes constructed with an atomically ordered intermetallic structure (O-PtCuNF/C) showing high ORR activity, durability, and chemical stability. We rationally designed the O-PtCuNF/C catalyst by combining theoretical composition predictions with a silica-coating-mediated synthesis. The O-PtCuNF/C combines intensified strain and ligand effects from the intermetallic PtCu L11 structure and advantages of the nanoframes, resulting in superior ORR activity to disordered alloy PtCu nanoframes (D-PtCuNF/C) and commercial Pt/C catalysts. Importantly, the O-PtCuNF/C showed the highest ORR mass activity among PtCu-based catalysts. Furthermore, the O-PtCuNF/C exhibited higher ORR durability and far less etching of constituent atoms than D-PtCuNF/C and Pt/C, attesting to the chemically stable nature of the intermetallic structure.