Heterogeneous Catalyst as a Functional Substrate Governing the Shape of Electrochemical Precipitates in Oxygen-Fueled Rechargeable Batteries.

Lithium-oxygen batteries have the potential to become the most eminent solution for future energy storage with their theoretical energy density exceeding all existing batteries. However, the insulating and insoluble discharge product (lithium peroxide; Li2O2) impairs practical application. Conventional catalyst designs based on the electronic structure and interfacial charge transfer descriptors have not been able to overcome these limitations due to Li2O2. Herein, we revisit the role of heterogeneous catalysts as substrates to regulate Li2O2 growth and the formation of solid/solid reaction interfaces. We demonstrate that controlled solid/solid interfacial structure design is a critical performance parameter beyond the inherent electronic structure. In particular, the Cu2O substrate in this study induces a homogeneous deposition of Pd atoms, which leads to well-controlled growth of Li2O2 resolving mass and charge transport limits (i.e., the bottleneck of oxygen reduction/evolution reactions), thus improving reversibility, capacity, and durability of the cells by dissipating electrochemical and mechanical stress. We thus verified the essential role of solid/solid interfaces to regulate the nucleation and growth process of Li2O2 in lithium-oxygen batteries.

Regulating Pseudo-Jahn-Teller Effect and Superstructure in Layered Cathode Materials for Reversible Alkali-Ion Intercalation.

The Jahn-Teller effect (JTE) is one of the most important determinators of how much stress layered cathode materials undergo during charge and discharge; however, many reports have shown that traces of superstructure exist in pristine layered materials and irreversible phase transitions occur even after eliminating the JTE. A careful consideration of the energy of cationic distortion using a Taylor expansion indicated that second-order JTE (pseudo-JTE) is more widespread than the aforementioned JTE because of the various bonding states that occur between bonding and antibonding molecular orbitals in transition-metal octahedra. As a model case, a P2-type Mn-rich cathode (Na3/4MnO2) was investigated in detail. MnO6 octahedra are well known to undergo either elongation or contraction in a specific direction due to JTE. Here, the substitution of Li for Mn (Na3/4(Li1/4Mn3/4)O2) helped to oxidize Mn3+ to Mn4+ suppressing JTE; however, the MnO6 octahedra remained asymmetric with a clear trace of the superstructure. With various advanced analyses, we disclose the pseudo-JTE as a general reason for the asymmetric distortions of the MnO6 octahedra. These distortions lead to the significant electrochemical degradation of Na3/4Li1/4Mn3/4O2. The suppression of the pseudo-JTE modulates phase transition behaviors during Na intercalation/deintercalation and thereby improves all of the electrochemical properties. The insight obtained by coupling a theoretical background for the pseudo-JTE with verified layered cathode material lattice changes implies that many previous approaches can be rationalized by regulating pseudo-JTE. This suggests that the pseudo-JTE should be thought more important than the well-known JTE for layered cathode materials.

Elucidating the charge storage mechanism of carbonaceous and organic electrode materials for sodium ion batteries.

Sodium ion batteries (SIB) have received much research attention in the past decades as they are considered to be one alternative to the currently prevalent lithium ion batteries, and carbonaceous and organic compounds present two promising classes of SIB electrode materials advantaged by abundance of their constituent elements and reduced environmental footprints. To accelerate the development of these materials for SIB applications, future research directions must be guided by a thorough understanding of the charge storage mechanism. This review presents recent efforts in mechanism elucidation for these two classes of SIB electrode materials since, compared to their inorganic counterparts, they have unique challenges in material analysis. Topics covered will include characterization techniques and analytical frameworks for mechanism elucidation, emphasizing the advantages and limitations of individual experimental methodologies and providing a commentary on scientific rigor in result interpretation.

Activating a Multielectron Reaction of NASICON-Structured Cathodes toward High Energy Density for Sodium-Ion Batteries.

The increasing demand to efficiently store and utilize the electricity from renewable energy resources in a sustainable way has boosted the request for sodium-ion battery technology due to the high abundance of sodium sources worldwide. Na superionic conductor (NASICON) structured cathodes with a robust polyanionic framework have been intriguing because of their open 3D structure and superior thermal stability. The ever-increasing demand for higher energy densities with NASICON-structured cathodes motivates us to activate multielectron reactions, thus utilizing the third sodium ion toward higher voltage and larger capacity, both of which have been the bottlenecks for commercializing sodium-ion batteries. A doping strategy with Cr inspired by first-principles calculations enables the activation of multielectron redox reactions of the redox couples V2+/V3+, V3+/V4+, and V4+/V5+, resulting in remarkably improved energy density even in comparison to the layer structured oxides and Prussian blue analogues. This work also comprehensively clarifies the role of the Cr dopant during sodium storage and the valence electron transition process of both V and Cr. Our findings highlight the importance of a broadly applicable doping strategy for achieving multielectron reactions of NASICON-type cathodes with higher energy densities in sodium-ion batteries.

Interface-Controlled Rhombohedral Li3V2(PO4)3 Embedded in Carbon Nanofibers with Ultrafast Kinetics for Li-Ion Batteries.

We present a unique composite assembly of rhombohedral Li3V2(PO4)3 and carbon nanofiber, which simultaneously facilitates Li-ion transport as well as electron transfer. For the synthesis of this composite, the inorganic precursors were confined in electron-spun nanofibers, and then, through controlled annealing, Na3V2(PO4)3 particulates were grown with controllable crystallite size and partially embedded into carbon nanofibers with precisely controlled diameter. The rhombohedral Li3V2(PO4)3 could be successfully obtained by ion exchange from Na to Li in the prepared Na3V2(PO4)3. The final rhombohedral Li3V2(PO4)3 particles anchored onto the carbon nanofibers exhibited excellent electrochemical performance with fast kinetics for Li-ion batteries. Suprisingly it maintains 69 and 41 mAh/g even at 100C as cathode and anode. Several advanced characterizations revealed that its ultrafast kinetics could be attributed to synergistic effect resulting from the distinctive microstructure of the composite and the structural superiority of highly symmetric rhombohedral Li3V2(PO4)3 over its monoclinic homologue for Li-ion transport.

Highly Reversible and Rapid Sodium Storage in GeP3 with Synergistic Effect from Outside-In Optimization.

The composite GeP3/C@rGO as a sodium ion battery anode material was fabricated by introducing a carbon matrix into GeP3 through high-energy ball milling, followed by encapsulating the resultant composite with graphene via a solution-based ultrasonic method. To delineate the individual role of carbon matrix and graphene, material characterization and electrochemical analyses were performed for GeP3/C@rGO and three other samples: bare GeP3, GeP3 with graphene coating (GeP3@rGO), and GeP3 with carbon matrix (GeP3/C). GeP3/C@rGO exhibits the highest electric conductivity (5.89 × 10-1 S cm-1) and the largest surface area (167.85 m2 g-1) among the four samples. The as-prepared GeP3/C@rGO delivered a reversible high capacity of 1084 mA h g-1 at 50 mA g-1, excellent rate capacity (435.4 mA h g-1 at a high rate of 5 A g-1), and long-term cycling stability (400 cycles with a reversible capacity of 823.3 mA h g-1 at 0.2 A g-1), all of which outperform the other three samples. The kinetics investigation reveals a "pseudocapacitive behavior" in GeP3/C and GeP3/C@rGO, where solely faradic reactions took place in bare GeP3 and GeP3@rGO with a typical "battery behavior". Based on ex-situ X-ray photoelectron spectroscopy and ex-situ electrochemical impedance spectroscopy, the carbon matrix serves to activate and stabilize the interior of the composite, while the graphene protects and restrains the exterior surface. Benefiting from the synergistic combination of these two components, GeP3/C@rGO achieved extremely stable cycling stability as well as outstanding rate performance.

Uncovering the Shuttle Effect in Organic Batteries and Counter-Strategies Thereof: A Case Study of the N,N'-Dimethylphenazine Cathode.

The main drawback of organic electrode materials is their solubility in the electrolyte, leading to the shuttle effect. Using N,N'-dimethylphenazine (DMPZ) as a highly soluble cathode material, and its PF6 - and triflimide salts as models for its first oxidation state, a poor correlation was found between solubility and battery operability. Extensive electrochemical experiments suggest that the shuttle effect is unlikely to be mediated by molecular diffusion as commonly understood, but rather by electron-hopping via the electron self-exchange reaction based on spectroscopic results. These findings led to two counter-strategies to prevent the hopping process: the pre-treatment of the anode to form a solid-electrolyte interface and using DMPZ salt rather than neutral DMPZ as the active material. These strategies improved coulombic efficiency and capacity retention, demonstrating that solubility of organic materials does not necessarily exclude their applications in batteries.

Unraveling the Structure of the Poly(triazine imide)/LiCl Photocatalyst: Cooperation of Facile Syntheses and a Low-Temperature Synchrotron Approach.

Graphitic carbon nitride (g-C3N4)-based materials have attracted interdisciplinary attention from many fields. However, their crystal structures have not yet been described well. Poly(triazine imide)/LiCl (PTI/LiCl) of good crystallinity synthesized from salt melts enables a confident structural solution for a better understanding of g-C3N4-based materials. In this study, we synthesize PTI/LiCl of high crystallinity in air without byproducts and confirm the orthorhombic feature, which is not observed in powder X-ray diffraction (PXRD) patterns at room temperature, by employing low-temperature synchrotron PXRD. Together with spectroscopic techniques (X-ray photoelectron spectroscopy, solid-state nuclear magnetic resonance, and Fourier-transform infrared/Raman), the orthorhombic structure (space group Cmc21, No. 36) was determined and found to be a superstructure of the previously reported hexagonal structure, as confirmed by electron diffraction. The temperature-dependent synchrotron PXRD data also reveal a highly anisotropic expansion. This work also shows the much higher activity of PTI/LiCl than of g-C3N4 for the photocatalytic degradation of methyl orange under ultraviolet irradiation, especially so for PTI/LiCl with a densely packed (001) plane. This study demonstrates the structural complexity of the g-C3N4 class of materials and illustrates how their temperature-dependent anisotropies facilitate the discovery of the structural features in resolving the structure of g-C3N4-related materials and their structure-property relationship.

Manganese based layered oxides with modulated electronic and thermodynamic properties for sodium ion batteries.

Manganese based layered oxides have received increasing attention as cathode materials for sodium ion batteries due to their high theoretical capacities and good sodium ion conductivities. However, the Jahn-Teller distortion arising from the manganese (III) centers destabilizes the host structure and deteriorates the cycling life. Herein, we report that zinc-doped Na0.833[Li0.25Mn0.75]O2 can not only suppress the Jahn-Teller effect but also reduce the inherent phase separations. The reduction of manganese (III) amount in the zinc-doped sample, as predicted by first-principles calculations, has been confirmed by its high binding energies and the reduced octahedral structural variations. In the viewpoint of thermodynamics, the zinc-doped sample has lower formation energy, more stable ground states, and fewer spinodal decomposition regions than those of the undoped sample, all of which make it charge or discharge without any phase transition. Hence, the zinc-doped sample shows superior cycling performance, demonstrating that zinc doping is an effective strategy for developing high-performance layered cathode materials.

Dark Photocatalysis: Storage of Solar Energy in Carbon Nitride for Time-Delayed Hydrogen Generation.

While natural photosynthesis serves as the model system for efficient charge separation and decoupling of redox reactions, bio-inspired artificial systems typically lack applicability owing to synthetic challenges and structural complexity. We present herein a simple and inexpensive system that, under solar irradiation, forms highly reductive radicals in the presence of an electron donor, with lifetimes exceeding the diurnal cycle. This radical species is formed within a cyanamide-functionalized polymeric network of heptazine units and can give off its trapped electrons in the dark to yield H2 , triggered by a co-catalyst, thus enabling the temporal decoupling of the light and dark reactions of photocatalytic hydrogen production through the radical's longevity. The system introduced here thus demonstrates a new approach for storing sunlight as long-lived radicals, and provides the structural basis for designing photocatalysts with long-lived photo-induced states.

Rational design of carbon nitride photocatalysts by identification of cyanamide defects as catalytically relevant sites.

The heptazine-based polymer melon (also known as graphitic carbon nitride, g-C3N4) is a promising photocatalyst for hydrogen evolution. Nonetheless, attempts to improve its inherently low activity are rarely based on rational approaches because of a lack of fundamental understanding of its mechanistic operation. Here we employ molecular heptazine-based model catalysts to identify the cyanamide moiety as a photocatalytically relevant 'defect'. We exploit this knowledge for the rational design of a carbon nitride polymer populated with cyanamide groups, yielding a material with 12 and 16 times the hydrogen evolution rate and apparent quantum efficiency (400 nm), respectively, compared with the unmodified melon. Computational modelling and material characterization suggest that this moiety improves coordination (and, in turn, charge transfer kinetics) to the platinum co-catalyst and enhances the separation of the photogenerated charge carriers. The demonstrated knowledge transfer for rational catalyst design presented here provides the conceptual framework for engineering high-performance heptazine-based photocatalysts.

Solar-Driven Reduction of Aqueous Protons Coupled to Selective Alcohol Oxidation with a Carbon Nitride-Molecular Ni Catalyst System.

Solar water-splitting represents an important strategy toward production of the storable and renewable fuel hydrogen. The water oxidation half-reaction typically proceeds with poor efficiency and produces the unprofitable and often damaging product, O2. Herein, we demonstrate an alternative approach and couple solar H2 generation with value-added organic substrate oxidation. Solar irradiation of a cyanamide surface-functionalized melon-type carbon nitride ((NCN)CNx) and a molecular nickel(II) bis(diphosphine) H2-evolution catalyst (NiP) enabled the production of H2 with concomitant selective oxidation of benzylic alcohols to aldehydes in high yield under purely aqueous conditions, at room temperature and ambient pressure. This one-pot system maintained its activity over 24 h, generating products in 1:1 stoichiometry, separated in the gas and solution phases. The (NCN)CNx-NiP system showed an activity of 763 µmol (g CNx)(-1) h(-1) toward H2 and aldehyde production, a Ni-based turnover frequency of 76 h(-1), and an external quantum efficiency of 15% (λ = 360 ± 10 nm). This precious metal-free and nontoxic photocatalytic system displays better performance than an analogous system containing platinum instead of NiP. Transient absorption spectroscopy revealed that the photoactivity of (NCN)CNx is due to efficient substrate oxidation of the material, which outweighs possible charge recombination compared to the nonfunctionalized melon-type carbon nitride. Photoexcited (NCN)CNx in the presence of an organic substrate can accumulate ultralong-lived "trapped electrons", which allow for fuel generation in the dark. The artificial photosynthetic system thereby catalyzes a closed redox cycle showing 100% atom economy and generates two value-added products, a solar chemical, and solar fuel.

Low-molecular-weight carbon nitrides for solar hydrogen evolution.

This work focuses on the control of the polymerization process for melon ("graphitic carbon nitride"), with the aim of improving its photocatalytic activity intrinsically. We demonstrate here that reduction of the synthesis temperature leads to a mixture of the monomer melem and its higher condensates. We show that this mixture can be separated and provide evidence that the higher condensates are isolated oligomers of melem. On evaluating their photocatalytic activity for hydrogen evolution, the oligomers were found to be the most active species, having up to twice the activity of the monomer/oligomer mixture of the as-synthesized material, which in turn has 3 times the activity of the polymer melon, the literature benchmark. These results highlight the role of "defects", i.e., chain terminations, in increasing the catalytic activity of carbon nitrides and at the same time point to the ample potential of intrinsically improving the photocatalytic activity of "carbon nitride", especially through the selective synthesis of the active phase.

Cationically charged Mn(II)Al(III) LDH nanosheets by chemical exfoliation and their use as building blocks in graphene oxide-based materials.

We report on the synthesis and exfoliation of Mn(II)Al(III) sulfonate and sulfate layered double hydroxides (LDHs) and their combination with graphene oxide by charge-directed self-assembly. The synthesis of the LDH compounds has been accomplished either directly by coprecipitation of the respective hydroxides with sulfonate anions or by ion-exchange of the chloride-containing LDH with sodium dodecylsulfate. Exfoliation of the bulk material in formamide yields colloidal suspensions of positively charged nanosheets with lateral dimensions of tens to hundreds of nanometers and thicknesses down to 1.3 nm, ascertained by TEM and AFM. Flocculation of the LDH nanosheets with an aqueous graphene oxide suspension yields a hybrid material that can be converted to a reduced graphene oxide/LDH composite by hydrazine reduction. The hybrid materials were tested for pseudocapacitive electrochemical storage capacity and electrocatalytic oxygen evolution reactions and showed significant increases compared to the pristine materials.

Ionic-liquid-mediated active-site control of MoS2 for the electrocatalytic hydrogen evolution reaction.

The layered crystal MoS(2) has been proposed as an alternative to noble metals as the electrocatalyst for the hydrogen evolution reaction (HER). However, the activity of this catalyst is limited by the number of available edge sites. It was previously shown that, by using an imidazolium ionic liquid as synthesis medium, nanometre-size crystal layers of MoS(2) can be prepared which exhibit a very high number of active edge sites as well as a de-layered morphology, both of which contribute to HER electrocatalytic activity. Herein, it is examined how to control these features synthetically by using a range of ionic liquids as synthesis media. Non-coordinating ILs with a planar heterocyclic cation produced MoS(2) with the de-layered morphology, which was subsequently shown to be highly advantageous for HER electrocatalytic activity. The results furthermore suggest that the crystallinity, and in turn the catalytic activity, of the MoS(2) layers can be improved by employing an IL with specific solvation properties. These results provide the basis for a synthetic strategy for increasing the HER electrocatalytic activity of MoS(2) by tuning its crystal properties, and thus improving its potential for use in hydrogen production technologies.

Tuning the photocatalytic activity of CdS nanocrystals through intermolecular interactions in ionic-liquid solvent systems.

Synthetic solvent systems for the fine-tuned preparation of CdS nanocrystallites, active in visible-light photocatalytic hydrogen production, were studied. To control crystallite size and spectral properties, the CdS crystals were synthesised by using different solvent systems, containing a series of tetrabutylammonium amino carboxylate ionic liquids as the crystal-growth control agents. Six samples of CdS, all with similar physical and spectral properties, exhibited greatly varying photocatalytic activity, with the most active sample outperforming the least active one by almost 60%. To rationalise this effect, the intermolecular interactions of the synthesis solvent system with the growing CdS nanocrystallites were characterised by using the Reichart betaine dye and the E(T)(N) polarity scale. A correlation was observed between the E(T)(N) values of the solvent system and the photocatalytic activity of the CdS nanocrystallite, suggesting that the hydrogen-bond-donating ability and/or dipolarity/polarisability interactions of the solvent system led to the preferential formation of active surfaces/surface sites on the CdS crystals.