Bridging Together Theoretical and Experimental Perspectives in Single-Atom Alloys for Electrochemical Ammonia Production.

Ammonia is an essential commodity in the food and chemical industry. Despite the energy-intensive nature, the Haber-Bosch process is the only player in ammonia production at large scales. Developing other strategies is highly desirable, as sustainable and decentralized ammonia production is crucial. Electrochemical ammonia production by directly reducing nitrogen and nitrogen-based moieties powered by renewable energy sources holds great potential. However, low ammonia production and selectivity rates hamper its utilization as a large-scale ammonia production process. Creating effective and selective catalysts for the electrochemical generation of ammonia is critical for long-term nitrogen fixation. Single-atom alloys (SAAs) have become a new class of materials with distinctive features that may be able to solve some of the problems with conventional heterogeneous catalysts. The design and optimization of SAAs for electrochemical ammonia generation have recently been significantly advanced. This comprehensive review discusses these advancements from theoretical and experimental research perspectives, offering a fundamental understanding of the development of SAAs for ammonia production.

Recent advances in food waste-derived nanoporous carbon for energy storage.

Affordable and environmentally friendly electrochemically active raw energy storage materials are in high demand to switch to mass-scale renewable energy. One particularly promising avenue is the feasibility of utilizing food waste-derived nanoporous carbon. This material holds significance due to its widespread availability, affordability, ease of processing, and, notably, its cost-free nature. Over the years, various strategies have been developed to convert different food wastes into nanoporous carbon materials with enhanced electrochemical properties. The electrochemical performance of these materials is influenced by both intrinsic factors, such as the composition of elements derived from the original food sources and recipes, and extrinsic factors, including the conditions during pyrolysis and activation. While current efforts are dedicated to optimizing process parameters to achieve superior performance in electrochemical energy storage devices, it is timely to take stock of the current state of research in this emerging field. This review provides a comprehensive overview of recent developments in the fabrication and surface characterisation of porous carbons from different food wastes. A special focus is given on the applications of these food waste derived porous carbons for energy storage applications including batteries and supercapacitors.

This review compiles very recent literature on the synthesis of porous carbon from food waste biomass and their efficient utilisation as electrode material for energy storage applications in supercapacitor devices.

Multifunctional carbon nitride nanoarchitectures for catalysis.

Catalysis is at the heart of modern-day chemical and pharmaceutical industries, and there is an urgent demand to develop metal-free, high surface area, and efficient catalysts in a scalable, reproducible and economic manner. Amongst the ever-expanding two-dimensional materials family, carbon nitride (CN) has emerged as the most researched material for catalytic applications due to its unique molecular structure with tunable visible range band gap, surface defects, basic sites, and nitrogen functionalities. These properties also endow it with anchoring capability with a large number of catalytically active sites and provide opportunities for doping, hybridization, sensitization, etc. To make considerable progress in the use of CN as a highly effective catalyst for various applications, it is critical to have an in-depth understanding of its synthesis, structure and surface sites. The present review provides an overview of the recent advances in synthetic approaches of CN, its physicochemical properties, and band gap engineering, with a focus on its exclusive usage in a variety of catalytic reactions, including hydrogen evolution reactions, overall water splitting, water oxidation, CO2 reduction, nitrogen reduction reactions, pollutant degradation, and organocatalysis. While the structural design and band gap engineering of catalysts are elaborated, the surface chemistry is dealt with in detail to demonstrate efficient catalytic performances. Burning challenges in catalytic design and future outlook are elucidated.

Creating Spin Channels in SrCoO3 through Triagonal-to-Cubic Structural Transformation for Enhanced Oxygen Evolution/Reduction Reactions.

Oxygen evolution and reduction reactions (OER and ORR) play crucial roles in energy conversion processes such as water splitting and air batteries, where spin dynamics inherently influence their efficiency. However, the specific contribution of spin has yet to be fully understood. In this study, we intentionally introduce a spin channel through the transformation of trigonal antiferromagnetic SrCoO2.5 into cubic ferromagnetic SrCoO3, aiming to deepen our understanding of spin dynamics in catalytic reactions. Based on the results from spherical-aberration-corrected microscope, synchrotron absorption spectra, magnetic characterizations, and density functional theory calculations, it is revealed that surface electron transfer is predominantly governed by local geometric structures, while the presence of the spin channel significantly enhances the bulk transport of spin-polarized electrons, particularly under high current densities where surface electron transfer is no longer the limiting factor. The overpotential for OER is reduced by at least 70 mV at 150 mA cm-2 due to the enhanced conductivity from spin-polarized electrons facilitated by spin channels, with an expectation of even more significant reductions at higher current densities. This work provides a clearer picture of the role of spin in oxygen-involved electrocatalysis, providing critical insights for the design of more efficient catalytic systems in practical applications.

Emerging Trends of Carbon-Based Quantum Dots: Nanoarchitectonics and Applications.

Carbon-based quantum dots (QDs) have emerged as a fascinating class of advanced materials with a unique combination of optoelectronic, biocompatible, and catalytic characteristics, apt for a plethora of applications ranging from electronic to photoelectrochemical devices. Recent research works have established carbon-based QDs for those frontline applications through improvements in materials design, processing, and device stability. This review broadly presents the recent progress in the synthesis of carbon-based QDs, including carbon QDs, graphene QDs, graphitic carbon nitride QDs and their heterostructures, as well as their salient applications. The synthesis methods of carbon-based QDs are first introduced, followed by an extensive discussion of the dependence of the device performance on the intrinsic properties and nanostructures of carbon-based QDs, aiming to present the general strategies for device designing with optimal performance. Furthermore, diverse applications of carbon-based QDs are presented, with an emphasis on the relationship between band alignment, charge transfer, and performance improvement. Among the applications discussed in this review, much focus is given to photo and electrocatalytic, energy storage and conversion, and bioapplications, which pose a grand challenge for rational materials and device designs. Finally, a summary is presented, and existing challenges and future directions are elaborated.

Strategies for Improving the Photocatalytic Hydrogen Evolution Reaction of Carbon Nitride-Based Catalysts.

Due to the depletion of fossil fuels and their-related environmental issues, sustainable, clean, and renewable energy is urgently needed to replace fossil fuel as the primary energy resource. Hydrogen is considered as one of the cleanest energies. Among the approaches to hydrogen production, photocatalysis is the most sustainable and renewable solar energy technique. Considering the low cost of fabrication, earth abundance, appropriate bandgap, and high performance, carbon nitride has attracted extensive attention as the catalyst for photocatalytic hydrogen production in the last two decades. In this review, the carbon nitride-based photocatalytic hydrogen production system, including the catalytic mechanism and the strategies for improving the photocatalytic performance is discussed. According to the photocatalytic processes, the strengthened mechanism of carbon nitride-based catalysts is particularly described in terms of boosting the excitation of electrons and holes, suppressing carriers recombination, and enhancing the utilization efficiency of photon-excited electron-hole. Finally, the current trends related to the screening design of superior photocatalytic hydrogen production systems are outlined, and the development direction of carbon nitride for hydrogen production is clarified.

Incorporation of Bimetallic Sulfide with Carbon Nitride for Advanced Na-Ion Batteries.

Sodium-ion batteries (SIBs) have received tremendous attention owing to their low cost, high working voltages, and energy density. However, the design and development of highly efficient SIBs represent a great challenge. Here, a unique and reliable approach is reported to prepare carbon nitride (CN) hybridized with nickel iron sulfide (NFCN) using simple reaction between Ni-Fe layered double hydroxide and dithiooxamide. The characterization results demonstrate that the hybridization with optimal amount of CN induces local distortion in the crystal structure of the hybrid, which would benefit SIB performance. Systematic electrochemical studies with a half-cell configuration show that the present hybrid structure exhibits a promising reversible specific capacity of 348 mAh g-1 at 0.1 A g-1 after 100 cycles with good rate capability. Simulation result reveals that the iron atoms in nickel iron sulfide act as a primary active site to accommodate Na+ ions. At last, with a full cell configuration using NFCN and Na3 V2 (PO4 )2 O2 F as the anode and cathode, respectively, the specific capacity appears to be ≈95 mAh g-1 after 50 cycles at 0.1 A g-1 condition. This excellent performance of these hybrids can be attributed to the synergistic effect of the incorporated CN species and the high conductivity of nickel-iron sulfide.

Realization of High Magnetization in Artificially Designed Ni/NiO Layers through Exchange Coupling.

High-magnetization materials play crucial roles in various applications. However, the past few decades have witnessed a stagnation in the discovery of new materials with high magnetization. In this work, Ni/NiO nanocomposites are fabricated by depositing Ni and NiO thin layers alternately, followed by annealing at specific temperatures. Both the as-deposited samples and those annealed at 373 K exhibit low magnetization. However, the samples annealed at 473 K exhibit a significantly enhanced saturation magnetization exceeding 607 emu cm-3 at room temperature, surpassing that of pure Ni (480 emu cm-3 ). Material characterizations indicate that the composite comprises NiO nanoclusters of size 1-2 nm embedded in the Ni matrix. This nanoclustered NiO is primarily responsible for the high magnetization, as confirmed by density functional theory calculations. The calculations also indicate that the NiO clusters are ferromagnetically coupled with Ni, resulting in enhanced magnetization. This work demonstrates a new route toward developing artificial high-magnetization materials using the high magnetic moments of nanoclustered antiferromagnetic materials.

Utilising the Nanozymatic Activity of Copper-Functionalised Mesoporous C3 N5 for Sensing Biomolecules.

Designing unique nanomaterials for the selective sensing of biomolecules is of significant interest in the field of nanobiotechnology. In this work, we demonstrated the synthesis of ordered Cu nanoparticle-functionalised mesoporous C3 N5 that has unique peroxidase-like nanozymatic activity for the ultrasensitive and selective detection of glucose and glutathione. A nano hard-templating technique together with the in-situ polymerisation and self-assembly of Cu and high N-containing CN precursor was adopted to introduce mesoporosity as well as high N and Cu content in mesoporous C3 N5 . Due to the ordered structure and highly dispersed Cu in the mesoporous C3 N5 , a large enhancement of the peroxidase mimetic activity in the oxidation of a redox dye in the presence of hydrogen peroxide could be obtained. Additionally, the optimised Cu-functionalised mesoporous C3 N5 exhibited excellent sensitivity to glutathione with a low detection limit of 2.0 ppm. The strong peroxidase activity of the Cu-functionalised mesoporous C3 N5 was also effectively used for the sensing of glucose with a detection limit of 0.4 mM through glucose oxidation with glucose oxidase. This unique Cu-functionalised mesoporous C3 N5 has the potential for detecting various molecules in the environment as well as for next-generation glucose and glutathione diagnostic devices.

Rare-Earth Doped Iron Oxide Nanostructures for Cancer Theranostics: Magnetic Hyperthermia and Magnetic Resonance Imaging.

Superparamagnetic iron oxide nanoparticles (SPIONs) have been extensively investigated during the last couple of decades because of their potential applications across various disciplines ranging from spintronics to nanotheranostics. However, pure iron oxide nanoparticles cannot meet the requirement for practical applications. Doping is considered as one of the most prominent and simplest techniques to achieve optimized multifunctional properties in nanomaterials. Doped iron oxides, particularly, rare-earth (RE) doped nanostructures have shown much-improved performance for a wide range of biomedical applications, including magnetic hyperthermia and magnetic resonance imaging (MRI), compared to pure iron oxide. Extensive investigations have revealed that bigger-sized RE ions possessing high magnetic moment and strong spin-orbit coupling can serve as promising dopants to significantly regulate the properties of iron oxides for advanced biomedical applications. This review provides a detailed investigation on the role of RE ions as primary dopants for engineering the structural and magnetic properties of Fe3 O4 nanoparticles to carefully introspect and correlate their impact on cancer theranostics with a special focus on magnetic hyperthermia and MRI. In addition, prospects for achieving high-performance magnetic hyperthermia and MRI are thoroughly discussed. Finally, suggestions on future work in these two areas are also proposed.

Low-Dimensional Metal-Halide Perovskites as High-Performance Materials for Memory Applications.

Metal-halide perovskites have drawn profuse attention during the past decade, owing to their excellent electrical and optical properties, facile synthesis, efficient energy conversion, and so on. Meanwhile, the development of information storage technologies and digital communications has fueled the demand for novel semiconductor materials. Low-dimensional perovskites have offered a new force to propel the developments of the memory field due to the excellent physical and electrical properties associated with the reduced dimensionality. In this review, the mechanisms, properties, as well as stability and performance of low-dimensional perovskite memories, involving both molecular-level perovskites and structure-level nanostructures, are comprehensively reviewed. The property-performance correlation is discussed in-depth, aiming to present effective strategies for designing memory devices based on this new class of high-performance materials. Finally, the existing challenges and future opportunities are presented.

Emerging trends in porous materials for CO2 capture and conversion.

The presence of an excessive concentration of CO2 in the atmosphere needs to be curbed with suitable measures including the reduction of CO2 emissions at stationary point sources such as power plants through carbon capture technologies and subsequent conversion of the captured CO2 into non-polluting clean fuels/chemicals using photo and/or electrocatalytic pathways. Porous materials have attracted much attention for carbon capture and in the recent past; they have witnessed significant advancements in their design and implementation for CO2 capture and conversion. In this context, the emerging trends in major porous adsorbents such as MOFs, zeolites, POPs, porous carbons, and mesoporous materials for CO2 capture and conversion are discussed. Their surface texture and chemistry, and the influence of various other features on their efficiency, selectivity, and recyclability for CO2 capture and conversion are explained and compared thoroughly. The scientific and technical advances on the material structure versus CO2 capture and conversion provide deep insights into designing effective porous materials. The review concludes with a summary, which compiles the key challenges in the field, current trends and critical challenges in the development of porous materials, and future research directions combined with possible solutions for realising the deployment of porous materials in CO2 capture and conversion.

Microporous Carbon Nitride (C3 N5.4 ) with Tetrazine based Molecular Structure for Efficient Adsorption of CO2 and Water.

Mesoporous carbon nitrides with C3 N5 and C3 N6 stoichiometries created a new momentum in the field of organic metal-free semiconductors owing to their unique band structures and high basicity. Here, we report on the preparation of a novel graphitic microporous carbon nitride with a tetrazine based chemical structure and the composition of C3 N5.4 using ultra-stable Y zeolite as the template and aminoguanidine hydrochloride, a high nitrogen-containing molecule, as the CN precursor. Spectroscopic characterization and density functional theory calculations reveal that the prepared material exhibits a new molecular structure, which comprises two tetrazines and one triazine rings in the unit cell and is thermodynamically stable. The resultant carbon nitride shows an outstanding surface area of 130.4 m2 g-1 and demonstrates excellent CO2 adsorption per unit surface area of 47.54 µmol m-2 , which is due to the existence of abundant free NH2 groups, basic sites and microporosity. The material also exhibits highly selective sensing over water molecules (151.1 mmol g-1 ) and aliphatic hydrocarbons due to its unique microporous structure with a high amount of hydrophilic nitrogen moieties and recognizing ability towards small molecules.

High Coercivity and Magnetization in WSe2 by Codoping Co and Nb.

Introducing ferromagnetism in transition metal dichalcogenides has attracted lots of attention due to the possible applications in spintronics devices. Generally, single magnetic element doping is used to introduce magnetism. However, mostly, weak ferromagnetism is observed. In this work, codoping of two kinds of transition metals (Nb and Co) into WSe2 is used to study its magnetic properties. In detail, single crystal WSe2 is codoped with 4 at% Co and various concentrations of Nb by employing the physical ion implantation method. Raman, X-ray diffraction and X-ray photoelectron spectroscopy results reveal the effective substitutional doping of implanted elements (Co and Nb). Magnetic measurements illustrate that both un-doped and 4 at% Co doped WSe2 show weak ferromagnetism whereas magnetization is strongly enhanced when Co and Nb are codoped into WSe2 . The magnetization is comparable with a ferromagnet, which may be attributed to Co, Nb doping and defects. In addition, a large coercivity of ≈1.2 kOe is observed in the 1 at% Nb-4 at% Co codoped WSe2 sample, which may be ascribed to the combined effect of doping-induced stress, defect-dictated pinning and anisotropy of NbSe bond owing to the charge transfer between Nb and Se ions.

Mixed Copper/Copper-Oxide Anchored Mesoporous Fullerene Nanohybrids as Superior Electrocatalysts toward Oxygen Reduction Reaction.

Developing a highly active, stable, and efficient non-noble metal-free functional electrocatalyst to supplant the benchmark Pt/C-based catalysts in practical fuel cell applications remains a stupendous challenge. A rational strategy is developed to directly anchor highly active and dispersed copper (Cu) nanospecies on mesoporous fullerenes (referred to as Cu-MFC60 ) toward enhancing oxygen reduction reaction (ORR) electrocatalysis. The preparation of Cu-MFC60 involves i) the synthesis of ordered MFC60 via the prevalent nanohard templating technique and ii) the postfunctionalization of MFC60 with finely distributed Cu nanospecies through incipient wet impregnation. The concurrence of Cu and cuprous oxide nanoparticles in the as-developed Cu-MFC60 samples through relevant material characterizations is affirmed. The optimized ORR catalyst, Cu(15%)-MFC60 , exhibits superior electrocatalytic ORR characteristics with an onset potential of 0.860 vs reversible hydrogen electrode, diffusion-limiting current density (-5.183 mA cm-2 ), improved stability, and tolerance to methanol crossover along with a high selectivity (four-electron transfer). This enhanced ORR performance can be attributed to the rapid mass transfer and abundant active sites owing to the synergistic coupling effects arising from the mixed copper nanospecies and the fullerene framework.

Gate-Tuned Interlayer Coupling in van der Waals Ferromagnet Fe_{3}GeTe_{2} Nanoflakes.

The weak interlayer coupling in van der Waals (vdW) magnets has confined their application to two dimensional (2D) spintronic devices. Here, we demonstrate that the interlayer coupling in a vdW magnet Fe_{3}GeTe_{2} (FGT) can be largely modulated by a protonic gate. With the increase of the protons intercalated among vdW layers, interlayer magnetic coupling increases. Because of the existence of antiferromagnetic layers in FGT nanoflakes, the increasing interlayer magnetic coupling induces exchange bias in protonated FGT nanoflakes. Most strikingly, a rarely seen zero-field cooled (ZFC) exchange bias with very large values (maximally up to 1.2 kOe) has been observed when higher positive voltages (V_{g}≥4.36 V) are applied to the protonic gate, which clearly demonstrates that a strong interlayer coupling is realized by proton intercalation. Such strong interlayer coupling will enable a wider range of applications for vdW magnets.

Aminotriazine derived N-doped mesoporous carbon with a tunable nitrogen content and their improved oxygen reduction reaction performance.

The electrocatalytic activity of carbon materials is highly dependent on the controlled modulation of their composition and porosity. Herein, mesoporous N-doped carbon with different amounts of nitrogen was synthesized through a unique strategy of using a high nitrogen containing CN precursor, 3-amino 1,2,4 triazine (3-ATZ) which is generally used for the preparation of carbon nitrides, integrated with the combination of a templating method and high temperature treatment. The nitrogen content and the graphitisation of the prepared materials were finely tuned with the simple adjustment of the carbonisation temperature (800-1100 °C). The optimised sample as an electrocatalyst for oxygen reduction reaction (ORR) exhibited an onset potential of 0.87 V vs. RHE with a current density of 5.1 mA cm-2 and a high kinetic current density (Jk) of 33.1 mA cm-2 at 0.55 V vs. RHE. The characterisation results of the prepared materials indicated that pyridinic and graphitic nitrogen in the carbon framework promoted ORR activity with improved four-electron selectivity and excellent methanol tolerance and stability. DFT calculations demonstrated that the structural and planar defects in the N-doped carbon regulated the surface electronic properties of the electrocatalyst, leading to a reduction in the energy barrier for the ORR activity. This strategy has the potential to unlock a platform for designing a series of catalysts for electrochemical applications.

Ultrathin High-Entropy Fe-Based Spinel Oxide Nanosheets with Metalloid Band Structures for Efficient Nitrate Reduction toward Ammonia.

Spinel oxides with tunable chemical compositions have emerged as versatile electrocatalysts, however their performance is greatly limited by small surface area and low electron conductivity. Here, ultrathin high-entropy Fe-based spinel oxides nanosheets are rationally designed (i.e., (Co0.2Ni0.2Zn0.2Mg0.2Cu0.2)Fe2O4; denotes A5Fe2O4) in thickness of ≈4.3 nm with large surface area and highly exposed active sites via a modified sol-gel method. Theoretic and experimental results confirm that the bandgap of A5Fe2O4 nanosheets is significantly smaller than that of ordinary Fe-based spinel oxides, realizing the transformation of binary spinel oxide from semiconductors to metalloids. As a result, such A5Fe2O4 nanosheets manifest excellent performance for the nitrate reduction reaction (NO3 -RR) to ammonia (NH3), with a NH3 yield rate of ≈2.1 mmol h-1 cm-2 at -0.5 V versus Reversible hydrogen electrode, outperforming other spinel-based electrocatalysts. Systematic mechanism investigations reveal that the NO3 -RR is mainly occurred on Fe sites, and introducing high-entropy compositions in tetrahedral sites regulates the adsorption strength of N and O-related intermediates on Fe for boosting the NO3 -RR. The above findings offer a high-entropy platform to regulate the bandgap and enhance the electrocatalytic performance of spinel oxides.

Robust Superconductivity in Infinite-Layer Nickelates.

The recent discovery of nickelate superconductivity represents an important step toward understanding the four-decade mastery of unconventional high-temperature superconductivity. However, the synthesis of the infinite-layer nickelate superconductors shows great challenges. Particularly, surface capping layers are usually unitized to facilitate the sample synthesis. This leads to an important question whether nickelate superconductors with d9 configuration and ultralow valence of Ni1+ are in metastable state and whether nickelate superconductivity can be robust? In this work, a series of redox cycling experiments are performed across the phase transition between perovskite Nd0.8Sr0.2NiO3 and infinite-layer Nd0.8Sr0.2NiO2. The infinite-layer Nd0.8Sr0.2NiO2 is quite robust in the redox environment and can survive the cycling experiments with unchanged crystallographic quality. However, as the cycling number goes on, the perovskite Nd0.8Sr0.2NiO3 shows structural degradation, suggesting stability of nickelate superconductivity is not restricted by the ultralow valence of Ni1+, but by the quality of its perovskite precursor. The observed robustness of infinite-layer Nd0.8Sr0.2NiO2 up to ten redox cycles further indicates that if an ideal high-quality perovskite precursor can be obtained, infinite-layer nickelate superconductivity can be very stable and sustainable under environmental conditions. This work provides important implications for potential device applications for nickelate superconductors.