Efficient Electrochemical Hydrogenation of Furfural to Furfuryl Alcohol Using an Anion-Exchange Membrane Electrolysis Cell.

The electrochemical hydrogenation (ECH) of furfural (FF) offers a promising pathway for the production of furfuryl alcohol (FA) while aligning with sustainability and environmental considerations. However, this technology has primarily been studied in half-cell configurations operating at high cell voltages and low current densities. Herein, we employ a membrane electrode assembly (MEA) system with an anion-exchange membrane for the ECH of FF and systematically investigate various parameters, including the ionomer content in the cathode catalyst, electrolyte type, electrolyte concentration, and flow rate. Under optimal conditions, our MEA system with non-noble metal-based catalysts exhibits a current density of 30 mA cm-2 with a Faradaic efficiency for FA production of 66% at a cell voltage of 2 V, maintaining operational durability for 5 h. This study highlights the potential of electrochemical FA production for practical applications to realize the decarbonization of the hydrogenation industry.

Improvement of Thermodynamic Phase Stability and High-Rate Capability of Li Layered Oxides.

The use of elemental doping in lithium cobalt oxide (LCO) cathode material at high cutoff voltage is a widely adopted technique in the field of rechargeable batteries to mitigate multiple unfavorable phase transitions. However, there is still a lack of fundamental understanding regarding the rationality of each doping element implemented in this method, specifically considering the various thermodynamic stability and phase transitions. Herein, we investigated the effect of Ti doping on an O2 phase LCO (LCTO) cathode material that exhibited enhanced rate performance. We suggest that the incorporation of Ti into an O2 phase LCO results in the mitigation of multiple-phase transitions and the improvement of phase stability, thereby yielding a high-rate-capable cathode material. Through a combination of experimental and computational calculations, we demonstrate that Ti doping improves the thermodynamic stability and kinetics of Li-ions during the cycling process.

Atom-Precise Heteroatom Core-Tailoring of Nanoclusters for Enhanced Solar Hydrogen Generation.

While core-shell nanomaterials are highly desirable for realizing enhanced optical and catalytic properties, their synthesis with atomic-level control is challenging. Here, the synthesis and crystal structure of [Au12 Ag32 (SePh)30 ]4- , the first example of selenolated Au-Ag core-shell nanoclusters, comprising a gold icosahedron core trapped in a silver dodecahedron, which is protected by an Ag12 (SePh)30 shell, is presented. The gold core strongly modifies the overall electronic structure and induces synergistic effects, resulting in high enhancements in the stability and near-infrared-II photoluminescence. The Au12 Ag32 and its homometal analog Ag44 , show strong interactions with oxygen vacancies of TiO2 , facilitating the interfacial charge transfer for photocatalysis. Indeed, the Au12 Ag32 /TiO2 exhibits remarkable solar H2 production (6810 µmol g-1  h-1 ), which is ≈6.2 and ≈37.8 times higher than that of Ag44 /TiO2 and TiO2 , respectively. Good stability and recyclability with minimal catalytic activity loss are additional features of Au12 Ag32 /TiO2 . The experimental and computational results reveal that the Au12 Ag32 acts as an efficient cocatalyst by possessing a favorable electronic structure that aligns well with the TiO2 bands for the enhanced separation of photoinduced charge carriers due to the relatively negatively charged Au12 core. These atomistic insights will motivate uncovering of the structure-catalytic activity relationships of other nanoclusters.

SiO-induced thermal instability and interplay between graphite and SiO in graphite/SiO composite anode.

Silicon monoxide (SiO), which exhibits better cyclability compared to silicon while delivering higher capacity than that of graphite, is an adequate material for the development of lithium-ion batteries (LIBs) having higher energy densities. However, incorporating silicon-based materials including SiO into stable graphite anode inevitably degrades not only cycle life but also calendar life of LIBs, while little is known about their aging mechanisms. Here, SiO-induced thermal instability of the graphite/SiO composite anode is investigated. We reveal that under thermal exposure, SiO accelerates the loss of lithium inventory and concomitantly facilitates the lithium de-intercalation from graphite. This self-discharge phenomenon, which is weakly observed in the graphite anode without SiO, is the result of preferential parasitic reaction on the SiO interface and spontaneous electron and lithium-ion migration to equilibrate the electron energy imbalance between graphite and SiO. Understanding this underlying electron-level interplay between graphite and SiO in the composite anode will contribute toward improving shelf life of SiO-containing LIBs in actual operating conditions.

Dynamic Electrochemical Interfaces for Energy Conversion and Storage.

Electrochemical energy conversion and storage are central to developing future renewable energy systems. For efficient energy utilization, both the performance and stability of electrochemical systems should be optimized in terms of the electrochemical interface. To achieve this goal, it is imperative to understand how a tailored electrode structure and electrolyte speciation can modify the electrochemical interface structure to improve its properties. However, most approaches describe the electrochemical interface in a static or frozen state. Although a simple static model has long been adopted to describe the electrochemical interface, atomic and molecular level pictures of the interface structure should be represented more dynamically to understand the key interactions. From this perspective, we highlight the importance of understanding the dynamics within an electrochemical interface in the process of designing highly functional and robust energy conversion and storage systems. For this purpose, we explore three unique classes of dynamic electrochemical interfaces: self-healing, active-site-hosted, and redox-mediated interfaces. These three cases of dynamic electrochemical interfaces focusing on active site regeneration collectively suggest that our understanding of electrochemical systems should not be limited to static models but instead expanded toward dynamic ones with close interactions between the electrode surface, dissolved active sites, soluble species, and reactants in the electrolyte. Only when we begin to comprehend the fundamentals of these dynamics through operando analyses can electrochemical conversion and storage systems be advanced to their full potential.

Design of a Metal/Oxide/Carbon Interface for Highly Active and Selective Electrocatalysis.

Sustainable energy-conversion and chemical-production require catalysts with high activity, durability, and product-selectivity. Metal/oxide hybrid structure has been intensively investigated to achieve promising catalytic performance, especially in neutral or alkaline electrocatalysis where water dissociation is promoted near the oxide surface for (de)protonation of intermediates. Although catalytic promise of the hybrid structure is demonstrated, it is still challenging to precisely modulate metal/oxide interfacial interactions on the nanoscale. Herein, we report an effective strategy to construct rich metal/oxide nano-interfaces on conductive carbon supports in a surfactant-free and self-terminated way. When compared to the physically mixed Pd/CeO2 system, a much higher degree of interface formation was identified with largely improved hydrogen oxidation reaction (HOR) kinetics. The benefits of the rich metal-CeO2 interface were further generalized to Pd alloys for optimized adsorption energy, where the Pd3Ni/CeO2/C catalyst shows superior performance with HOR selectivity against CO poisoning and shows long-term stability. We believe this work highlights the importance of controlling the interfacial junctions of the electrocatalyst in simultaneously achieving enhanced activity, selectivity, and stability.

Surface Electrochemistry of Carbon Electrodes and Faradaic Reactions in Capacitive Deionization.

Recent advances in electrochemical desalination techniques have paved way for utilization of saline water. In particular, capacitive deionization (CDI) enables removal of salts with high energy efficiency and economic feasibility, while its applicability has been challenged by degradation of carbon electrodes in long-term operations. Herein, we report a thorough investigation on the surface electrochemistry of carbon electrodes and Faradaic reactions that are responsible for stability issues of CDI systems. By using bare and membrane CDI (MCDI) as model systems, we identified various electrochemical reactions of carbon electrodes with water or oxygen, with thermodynamics and kinetics governed by the electrode potential and pH. As a result, a complete overview of the Faradaic reactions taking place in CDI was constructed by tracing the physicochemical changes occurring in CDI and MCDI systems.

Effect of Precursor Status on the Transition from Complex to Carbon Shell in a Platinum Core-Carbon Shell Catalyst.

Encapsulating platinum nanoparticles with a carbon shell can increase the stability of core platinum nanoparticles by preventing their dissolution and agglomeration. In this study, the synthesis mechanism of a platinum core-carbon shell catalyst via thermal reduction of a platinum-aniline complex was investigated to determine how the carbon shell forms and identify the key factor determining the properties of the Pt core-carbon shell catalyst. Three catalysts originating from the complexes with different platinum to carbon precursor ratios were synthesized through pyrolysis. Their structural characteristics were examined using various analysis techniques, and their electrochemical activity and stability were evaluated through half-cell and unit-cell tests. The relationship between the nitrogen to platinum ratio and structural characteristics was revealed, and the effects on the electrochemical activity and stability were discussed. The ratio of the carbon precursor to platinum was the decisive factor determining the properties of the platinum core-carbon shell catalyst.

Carbon Shell on Active Nanocatalyst for Stable Electrocatalysis.

Electrocatalysis is a key process for renewable energy conversion and fuel production in future energy systems. Various nanostructures have been investigated to optimize the electrocatalytic activity and realize efficient energy use. However, the long-term stability of electrocatalysts is also crucial for the sustainable and reliable operation of energy devices. Nanocatalysts are degraded by various processes during electrocatalysis, which causes critical performance loss. Recent operando analyses have revealed the mechanisms of electrocatalyst failure, and specific structures have been identified as robust against degradation. Nevertheless, achieving both high activity and robust stability with the same nanostructure is challenging because the structure-property relationships that affect activity and stability are different. The optimization of electrocatalysis is often limited by a large trade-off between activity and stability in catalyst structures. Therefore, it is essential to introduce functional structural units into catalyst design to achieve electrochemical stability while preserving high activity.In this Account, we highlight the strategic use of carbon shells on catalyst surfaces to improve the stability during electrocatalysis. For this purpose, we cover three issues in the use of carbon-shell-encapsulated nanoparticles (CSENPs) as robust and active electrocatalysts: the origin of the improved stability, the identification of active sites, and synthetic routes. Carbon shells can shield catalyst surfaces from both (electro)chemical oxidation and physical agglomeration. By limiting the exposure of the catalyst surface to an oxidizing (electro)chemical environment, carbon shells can preserve the initial active site structure during electrocatalysis. In addition, by providing a physical barrier between nanoparticles, carbon shells can maintain the high surface area of CSENPs by reducing particle agglomeration during electrocatalysis. This barrier effect is also useful for constructing more active or durable structures by annealing without surface area loss. Compared to the clear stabilizing effect, however, the effect of the shell on active sites on the CSENP surface can be puzzling. Even when they are covered by a carbon shell that can block molecular adsorption on active sites, CSENP catalysts remain active and even exhibit unique catalytic behavior. Thus, we briefly cover recent efforts to identify major active sites on CSENPs using molecular probes. Furthermore, considering the membranelike role of the carbon shell, we suggest several remaining issues that should be resolved to obtain a fundamental understanding of CSENP design. Finally, we describe two synthetic approaches for the successful carbon shell encapsulation of nanoparticles: two-step and one-step syntheses. Both the postmortem coating of nanocatalysts (two-step) and the in situ formation via precursor ligands (one step) are shown to produce a durable carbon layer on nanocatalysts in a controlled manner. The strengths and limitations of each approach are also presented to promote the further investigation of advanced synthesis methods.The hybrid structure of CSENPs, that is, the active catalyst surface and the durable carbon shell, provides an interesting opportunity in electrocatalysis. However, our understanding of CSENPs is still highly limited, and further investigation is needed to answer fundamental questions regarding both active site identification and the mechanisms of stability improvement. Only when we start to comprehend the fundamental mechanisms underlying electrocatalysis on CSENPs will electrocatalysts be further improved for sustainable long-term device operation.

Hierarchically Structured Conductive Polymer Binders with Silver Nanowires for High-Performance Silicon Anodes in Lithium-Ion Batteries.

Silicon (Si) anodes in lithium-ion batteries (LIBs) suffer from huge volume changes that lead to a rapid capacity decrease and short cycle life. A conductive binder can be a key factor to overcome this issue, maintaining continuous electron paths under pulverization of Si. Herein, composites of poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) and poly(vinyl alcohol) (PVA) are augmented with poly(ethylene glycol) (PEG) and poly(ethylene oxide) (PEO) as a binder for Si anodes, which forms hierarchical structures due to different chain lengths of PEG and PEO. The integration of PEG and PEO imparts higher electrical conductivity (∼40%) and stretchability (∼60%) through densely spread hydrogen bonding and cross-linking, compared to conductive polymer binders with PEO or PEG. Further, a silver nanowire (AgNW) network combined with the polymer binder supplies an effective three-dimensional (3D) electrical path, sufficient void space to buffer the volume changes, and highly adhesive interaction with the current collector. The fabricated Si anode demonstrates a higher specific capacity of 1066 mAh g-1 at 0.8 A g-1 after 100 cycles and improved rate capability.

Facet-Defined Strain-Free Spinel Oxide for Oxygen Reduction.

Exposing facet and surface strain are critical factors affecting catalytic performance but unraveling the composition-dependent activity on specific facets under strain-controlled environment is still challenging due to the synthetic difficulties. Herein, we achieved a (001) facet-defined Co-Mn spinel oxide surface with different surface compositions using epitaxial growth on Co3O4 nanocube template. We adopted composition gradient synthesis to relieve the strain layer by layer, minimizing the surface strain effect on catalytic activity. In this system, experimental and calculational analyses of model oxygen reduction reaction (ORR) activity reveals a volcano-like trend with Mn/Co ratios because of an adequate charge transfer from octahedral-Mn to neighboring Co. Co0.5Mn0.5 as an optimized Mn/Co ratio exhibits both outstanding ORR activity (0.894 V vs RHE in 1 M KOH) and stability (2% activity loss against chronoamperometry). By controlling facet and strain, this study provides a well-defined platform for investigating composition-structure-activity relationships in electrocatalytic processes.

Structural Insights into Multi-Metal Spinel Oxide Nanoparticles for Boosting Oxygen Reduction Electrocatalysis.

Multi-metal oxide (MMO) materials have significant potential to facilitate various demanding reactions by providing additional degrees of freedom in catalyst design. However, a fundamental understanding of the (electro)catalytic activity of MMOs is limited because of the intrinsic complexity of their multi-element nature. Additional complexities arise when MMO catalysts have crystalline structures with two different metal site occupancies, such as the spinel structure, which makes it more challenging to investigate the origin of the (electro)catalytic activity of MMOs. Here, uniform-sized multi-metal spinel oxide nanoparticles composed of Mn, Co, and Fe as model MMO electrocatalysts are synthesized and the contributions of each element to the structural flexibility of the spinel oxides are systematically studied, which boosts the electrocatalytic oxygen reduction reaction (ORR) activity. Detailed crystal and electronic structure characterizations combined with electrochemical and computational studies reveal that the incorporation of Co not only increases the preferential octahedral site occupancy, but also modifies the electronic state of the ORR-active Mn site to enhance the intrinsic ORR activity. As a result, nanoparticles of the optimized catalyst, Co0.25 Mn0.75 Fe2.0 -MMO, exhibit a half-wave potential of 0.904 V (versus RHE) and mass activity of 46.9 A goxide -1 (at 0.9 V versus RHE) with promising stability.

Differences in the Electrochemical Performance of Pt-Based Catalysts Used for Polymer Electrolyte Membrane Fuel Cells in Liquid Half- and Full-Cells.

A substantial amount of research effort has been directed toward the development of Pt-based catalysts with higher performance and durability than conventional polycrystalline Pt nanoparticles to achieve high-power and innovative energy conversion systems. Currently, attention has been paid toward expanding the electrochemically active surface area (ECSA) of catalysts and increase their intrinsic activity in the oxygen reduction reaction (ORR). However, despite innumerable efforts having been carried out to explore this possibility, most of these achievements have focused on the rotating disk electrode (RDE) in half-cells, and relatively few results have been adaptable to membrane electrode assemblies (MEAs) in full-cells, which is the actual operating condition of fuel cells. Thus, it is uncertain whether these advanced catalysts can be used as a substitute in practical fuel cell applications, and an improvement in the catalytic performance in real-life fuel cells is still necessary. Therefore, from a more practical and industrial point of view, the goal of this review is to compare the ORR catalyst performance and durability in half- and full-cells, providing a differentiated approach to the durability concerns in half- and full-cells, and share new perspectives for strategic designs used to induce additional performance in full-cell devices.

Effects of Photochemical Oxidation of the Carbonaceous Additives on Li-S Cell Performance.

We introduce a simple and easy way to functionalize the surface of various carbonaceous materials through the ultraviolet light/ozone (UV/O3) plasma where we utilize the zero-, one-, and two-dimensional carbon frameworks. In a general manner, the lamps of a UV/O3 generator create two different wavelengths (λ = 185 and 254 nm); the shorter wavelength (λ = 185 nm) dissociates the oxygen (O2) in air and the longer wavelength (λ = 254 nm) dissociates the O3 and creates the reactive and monoatomic oxygen radical, which tends to incorporate onto the defects of the carbons. By tailoring the association and dissociation of the oxygen with various forms, carbon black, carbon nanofibers, and graphite flakes, chosen as representative models for the zero-, one-, and two-dimensional carbon frameworks, their structure can be oxidized, respectively, which is known as photochemical oxidation. Various carbons have their own distinctive morphology and electron transport properties, which are applicable for the lithium-sulfur (Li-S) cell. We, here, report on the improvement of electrochemical performance of the lithium/sulfur cell through such an efficient functionalization approach.

Amphiphilic Ti porous transport layer for highly effective PEM unitized regenerative fuel cells.

Polymer electrolyte membrane unitized regenerative fuel cells (PEM-URFCs) require bifunctional porous transport layers (PTLs) to play contradictory roles in a single unitized system: hydrophobicity for water drainage in the fuel cell (FC) mode and hydrophilicity for water supplement in the electrolysis cell (EC) mode. Here, we report a high-performance amphiphilic Ti PTL suitable for both FC and EC modes, thanks to alternating hydrophobic and hydrophilic channels. To fabricate the amphiphilic PTL, we used a shadow mask patterning process using ultrathin polydimethylsiloxane (PDMS) brush as a hydrophobic surface modifier, which can change the Ti PTL's surface polarity without decreasing its electrical conductivity. Consequently, performance improved by 4.3 times in FC (@ 0.6 V) and 1.9 times in EC (@ 1.8 V) from amphiphilic PTL. To elucidate reason for performance enhancement, discrete gas emission through the hydrophobic channels in amphiphilic PTL was verified under scanning electrochemical microscopy.

Self-supported mesoscopic tin oxide nanofilms for electrocatalytic reduction of carbon dioxide to formate.

Here we report a self-supported SnO2 nanofilm prepared by a robust electrochemical process as an electrocatalyst for the CO2 reduction reaction. The SnO2 film had a large surface area originating from its nano-architecture and manifested high selectivity toward formate (over 60%), which resulted in CO2-to-formate current density up to 33.66 mA cm-2 that is among the state-of-the-art. We unveiled that the high performance of the SnO2 nanofilm is attributable to the presence of a metastable oxide under reductive conditions in addition to the abovementioned advantages.

Methanol Tolerant Pt-C Core-Shell Cathode Catalyst for Direct Methanol Fuel Cells.

Methanol crossover is one of the largest problems in direct methanol fuel cells (DMFCs). Methanol passing from the anode to the cathode through the membrane is oxidized at the cathode, degrading the DMFC performance, and the intermediates of the methanol oxidation reaction (MOR) cause cathode catalyst poisoning. Therefore, it is essential to develop a cathode catalyst capable of inhibiting MOR while promoting the oxygen reduction reaction (ORR), which is a typical cathode reaction in DMFCs. In this study, a carbon-encapsulated Pt cathode catalyst was synthesized for this purpose. The catalyst was simply synthesized by heat treatment of Pt-aniline complex-coated carbon nanofibers. The carbon shell of the catalyst was effective in inhibiting methanol from accessing the Pt core, and this effect became more prominent as the graphitization degree of the carbon shell increased. Meanwhile, the carbon shell allowed O2 to permeate regardless of the graphitization degree, enabling the Pt core to participate in ORR. The synthesized catalyst showed higher performance and stability in single-cell tests under various conditions compared to commercial Pt/C.

Direct Synthesis of Intermetallic Platinum-Alloy Nanoparticles Highly Loaded on Carbon Supports for Efficient Electrocatalysis.

Compared to nanostructured platinum (Pt) catalysts, ordered Pt-based intermetallic nanoparticles supported on a carbon substrate exhibit much enhanced catalytic performance, especially in fuel cell electrocatalysis. However, direct synthesis of homogeneous intermetallic alloy nanocatalysts on carbonaceous supports with high loading is still challenging. Herein, we report a novel synthetic strategy to directly produce highly dispersed MPt alloy nanoparticles (M = Fe, Co, or Ni) on various carbon supports with high catalyst loading. Importantly, a unique bimetallic compound, composed of [M(bpy)3]2+ cation (bpy = 2,2'-bipyridine) and [PtCl6]2- anion, evenly decomposes on carbon surface and forms uniformly sized intermetallic nanoparticles with a nitrogen-doped carbon protection layer. The excellent oxygen reduction reaction (ORR) activity and stability of the representative reduced graphene oxide (rGO)-supported L10-FePt catalyst (37 wt %-FePt/rGO), exhibiting 18.8 times higher specific activity than commercial Pt/C catalyst without degradation over 20 000 cycles, well demonstrate the effectiveness of our synthetic approach toward uniformly alloyed nanoparticles with high homogeneity.

Structural and Thermodynamic Understandings in Mn-Based Sodium Layered Oxides during Anionic Redox.

A breakthrough utilizing an anionic redox reaction (O2-/On-) for charge compensation has led to the development of high-energy cathode materials in sodium-ion batteries. However, its reaction results in a large voltage hysteresis due to the structural degradation arising from an oxygen loss. Herein, an interesting P2-type Mn-based compound exhibits a distinct two-phase behavior preserving a high-potential anionic redox (≈4.2 V vs Na+/Na) even during the subsequent cycling. Through a systematic series of experimental characterizations and theoretical calculations, the anionic redox reaction originating from O 2p-electron and the reversible unmixing of Na-rich and Na-poor phases are confirmed in detail. In light of the combined study, a critical role of the anion-redox-induced two-phase reaction in the positive-negative point of view is demonstrated, suggesting a rational design principle considering the phase separation and lattice mismatch. Furthermore, these results provide an exciting approach for utilizing the high-voltage feature in Mn-based layered cathode materials that are charge-compensated by an anionic redox reaction.

Design considerations for lithium-sulfur batteries: mass transport of lithium polysulfides.

Irreversible loss of soluble lithium polysulfides (LiPSs) is a major obstacle deteriorating the performance of lithium-sulfur batteries. Multiple innovative approaches have recently been developed to resolve these LiPS issues. Melt-diffusion of sulfur into porous carbon is a representative solution for preventing the diffusion out of LiPSs, which aims to coordinate the sulfur on the electrochemically active site, accordingly. However, it has been overlooked that the mass transport motion of LiPSs has a crucial role in achieving high-performance. In this paper, we highlight the importance of the mass transport of soluble sulfur in the cathode structure by introducing various starting materials, i.e., solid sulfur using melt-diffusion and a catholyte, using 3-dimensional ordered macroporous carbon. The capacity of the sulfur cathode using melt-diffusion is well conserved in carbon with small pores because LiPSs are slowly diffused away, however, the catholyte derived sulfur cathode shows superior performance in carbon with large pores due to their rapid mass transport. The comparison with the four different combinations that control the pore size and mass transport reveals that proper selection of the initial state of starting materials using porous carbons demonstrates the optimal cell performance.