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Abstract In this study, a simple thermal reduction process is used to synthesize a rGO-Ca2Fe2O5 (rGO-CFO) nanocomposite, with the morphological and optical characteristics of the CFO nanomaterial being modified by the rGO incorporation. The interface between rGO nanosheets and CFO nanoparticles facilitates efficient charge separation and resulting transfer of photogenerated charge carriers across the rGO nanosheets, demonstrated from photoluminescence and Mott-Schottky tests. Compared to CFO (2.1 eV), rGO-CFO has a reduced band gap energy of 1.9 eV. As synthesized nanocomposites were initially optimized and utilized for photodegradation of organic effluent Methylene blue (MB). An addition of 5 wt% rGO to the CFO demonstrated an improved photodegradation efficiency (97%) compared to bare CFO (72%). An active species trapping experiment was used to assess the MB photodegradation mechanism. The results demonstrate that hydroxyl radicals and holes are the major active species involved in photodegradation. The optimized composition (5rGO-CFO) was further tested for degradation of Bisphenol-A and Tetracycline (antibiotic). Altogether, these investigations show that the rGO-CFO is a highly efficient photocatalyst that can be used to remediate emerging contaminants in sunlight.

Abstract On-surface synthesis provides tools to prepare low-dimensional supramolecular structures. Traditionally, reactive radicals are a class of single-electron species, serving as exceptional electron-withdrawing groups. On metal surfaces, however, such species are affected by conduction band screening effects that may even quench their unpaired electron characteristics. As a result, radicals are expected to be less active, and reactions catalyzed by surface-stabilized radicals are rarely reported. Herein, we describe a class of inter-molecular radical transfer reactions on metal surfaces. With the assistance of aryl halide precursors, the coupling of terminal alkynes is steered from non-dehydrogenated to dehydrogenated products, resulting in alkynyl-Ag-alkynyl bonds. Dehalogenated molecules are fully passivated by detached hydrogen atoms. The reaction mechanism is unraveled by various surface-sensitive technologies and density functional theory calculations. Moreover, we reveal the universality of this mechanism on metal surfaces. Our studies enrich the on-surface synthesis toolbox and develop a pathway for producing low-dimensional organic materials.

Abstract Aqueous zinc‐ion batteries (AZIBs) based on vanadium oxides or sulfides are promising candidates for large‐scale rechargeable energy storage due to their ease of fabrication, low cost, and high safety. However, the commercial application of vanadium‐based electrode materials has been hindered by challenging problems such as poor cyclability and low‐rate performance. To this regard, sophisticated nanostructure engineering technology is used to adeptly incorporate VS2 nanosheets into the MXene interlayers to create a stable 2D heterogeneous layered structure. The MXene nanosheets exhibit stable interactions with VS2 nanosheets, while intercalation between nanosheets effectively increases the interlayer spacing, further enhancing their stability in AZIBs. Benefiting from the heterogeneous layered structure with high conductivity, excellent electron/ion transport, and abundant reactive sites, the free‐standing VS2/Ti3C2Tz composite film can be used as both the cathode and the anode of AZIBs. Specifically, the VS2/Ti3C2Tz cathode presents a high specific capacity of 285 mAh g−1 at 0.2 A g−1. Furthermore, the flexible Zn‐metal free in‐plane VS2/Ti3C2Tz//MnO2/CNT AZIBs deliver high operation voltage (2.0 V) and impressive long‐term cycling stability (with a capacity retention of 97% after 5000 cycles) which outperforms almost all reported Vanadium‐based electrodes for AZIBs. The effective modulation of the material structure through nanocomposite engineering effectively enhances the stability of VS2, which shows great potential in Zn2+ storage. This work will hasten and stimulate further development of such composite material in the direction of energy storage.

Abstract The combination of the ability to absorb most of the solar radiation and simultaneously suppress infrared re-radiation allows selective solar absorbers (SSAs) to maximize solar energy to heat conversion, which is critical to several advanced applications. The intrinsic spectral selective materials are rare in nature and only a few demonstrated complete solar absorption. Typically, intrinsic materials exhibit high performances when integrated into complex multilayered solar absorber systems due to their limited spectral selectivity and solar absorption. In this study, we propose CoSbx (2

Abstract Although perovskite light-emitting diodes (PeLEDs) have seen unprecedented development in device efficiency over the past decade, they suffer significantly from poor operational stability. This is especially true for blue PeLEDs, whose operational lifetime remains orders of magnitude behind their green and red counterparts. Here, we systematically investigate this efficiency-stability discrepancy in a series of green- to blue-emitting PeLEDs based on mixed Br/Cl-perovskites. We find that chloride incorporation, while having only a limited impact on efficiency, detrimentally affects device stability even in small amounts. Device lifetime drops exponentially with increasing Cl-content, accompanied by an increased rate of change in electrical properties during operation. We ascribe this phenomenon to an increased mobility of halogen ions in the mixed-halide lattice due to an increased chemically and structurally disordered landscape with reduced migration barriers. Our results indicate that the stability enhancement for PeLEDs might require different strategies from those used for improving efficiency. Graphical Abstract

Enetriynes, which belong to the enyne family, are characterized by a distinct electron-rich carbon-bonding scheme. Here, the authors report the formation of enetriynes with high selectivity by tetramerization of terminal alkynes on Ag(100).

Abstract A desired prerequisite when performing a quantum mechanical calculation is to have an initial idea of the atomic positions within an approximate crystal structure. The atomic positions combined should result in a system located in, or close to, an energy minimum. However, designing low-energy structures may be a challenging task when prior knowledge is scarce, specifically for large multi-component systems where the degrees of freedom are close to infinite. In this paper, we propose a method for identification of low-energy crystal structures within multi-component systems by combining cluster expansion and crystal structure predictions with density-functional theory calculations. Crystal structure prediction searches are applied to the Mo2AlB2 and Sc2AlB2 ternary systems to identify candidate structures, which are subsequently used to explore the quaternary (pseudo-binary) (Mo x Sc1–x )2AlB2 system through the cluster expansion formalism utilizing the ground-state search approach. Furthermore, we show that utilizing low-energy structures found within the cluster expansion ground-state search as seed structures within crystal structure predictions of (Mo x Sc1–x )2AlB2 can significantly reduce the computational demands. With this combined approach, we not only correctly identified the recently discovered Mo4/3Sc2/3AlB2 i-MAB phase, comprised of in-plane chemical ordering of Mo and Sc and with Al in a Kagomé lattice, but also predict additional low-energy structures at various concentrations. This result demonstrates that combining crystal structure prediction with cluster expansion provides a path for identifying low-energy crystal structures in multi-component systems by employing the strengths from both frameworks.

Abstract The factors controlling the top-down synthesis of MXenes, by selectively removing the A elements from parent MAX phases, is still under debate. In particular, understanding why some MAX phases can be used for creating MXenes, while others cannot, is of immense interest and would greatly support computational screening and identification of new two-dimensional materials that could also be created by chemical exfoliation. Here we computationally study the etching of MAX phases in hydrofluoric acid, considering the complete exfoliation process and competing processes during the initial steps of the synthesis. The results are compared to experiments and MAX phases successfully converted to MXenes, as well as so far unsuccessful attempts, including previously unpublished experimental data, rationalizing why some MAX phases are exfoliable while others are not. Our results provide an improved understanding of the synthesis of MXenes under acid conditions, anticipated to be vital for our ability to discover novel two-dimensional materials.

Despite their vast potential, the practical deployment of MXenes has been hampered by their tendency to be oxidized. Here, the authors show that simply vibrating MXene films in just a minute can remove the oxide layer formed and restore their electrochemical performance close to its original state.

Intercalation of noble metals into non-van der Waals solids provides a new avenue to synthesize novel nanolaminated compounds with distinct material properties. Herein, we use solid-state reaction at 400 °C to prepare Cr2AuC from two Cr-based Mn+1AXn phase precursors and demonstrate the formation of Cr2AuC upon full replacement of Ga layers with Au in Cr2GaC thin films via thermal substitution reaction. The resulting Cr2AuC exhibits 2.7% lattice expansion relative to the original Cr2GaC, whereas Ge in a Cr2GeC thin film was sparsely replaced by Au, as revealed by electron microscopy and x-ray diffraction analysis. To explain the observed differences, using ab initio calculations, we consider the bonding properties of Cr2GaC and Cr2GeC, and the energetic driving forces for substitution by evaluating the mixing free energy of Au on both A-sites of the MAX phases, and of both A-elements in the surrounding Au lattice. The results suggest that it is somewhat easier to mix Au on the A-site in Cr2GaC than in Cr2GeC, and substantially easier to mix Ga into the Au-lattice than Ge. Finally, we discuss how the gained insights can be consulted for exploring a wider class of Mn+1AXn phases with intercalated noble metals.

Recently, we presented a family of in-plane chemically ordered transition metal borides of the general formula (M′2/3M′′1/3)2AlB2. Here, we investigate incorporation of magnetic rare earth (RE) elements into this structure by synthesis and analysis of Mo4/3RE2/3AlB2, where RE = Ho, Tb, and Er. The crystal structure is verified by X-ray diffraction and scanning transmission electron microscopy, while the composition is derived from energy dispersive X-ray analysis. Through magnetization measurements, we also show that Mo4/3Ho2/3AlB2 orders antiferromagnetically below 9 K. We suggest that (M′2/3M′′1/3)2AlB2 could potentially be a versatile platform for new magnetic materials, in 3D as well as 2D.

Abstract On‐surface synthesis has recently emerged as a powerful strategy to design conjugated polymers previously precluded in conventional solution chemistry. Here, an N‐containing pentacene‐based precursor (tetraazapentacene) is ex‐professo synthesized endowed with terminal dibromomethylene (:CBr2) groups to steer homocoupling via dehalogenation on metallic supports. Combined scanning probe microscopy investigations complemented by theoretical calculations reveal how the substrate selection drives different reaction mechanisms. On Ag(111) the dissociation of bromine atoms at room temperature triggers the homocoupling of tetraazapentacene units together with the binding of silver adatoms to the nitrogen atoms of the monomers giving rise to a N‐containing conjugated coordination polymer (P1). Subsequently, P1 undergoes ladderization at 200 °C, affording a pyrrolopyrrole‐bridged conjugated polymer (P2). On Au(111) the formation of the intermediate polymer P1 is not observed and, instead, after annealing at 100 °C, the conjugated ladder polymer P2 is obtained, revealing the crucial role of metal adatoms on Ag(111) as compared to Au(111). Finally, on Ag(100) the loss of :CBr2 groups affords the formation of tetraazapentacene monomers, which coexist with polymer P1. Our results contribute to introduce protocols for the synthesis of N‐containing conjugated polymers, illustrating the selective role of the metallic support in the underlying reaction mechanisms.

High-entropy (HE) MXenes are a new emerging class of materials with unique properties, diverse compositions, and potential uses in energy storage devices. Herein, high-entropy MXene, Ti1.1V0.7CrxNb1.0Ta0.6C3Tz (Tz = –F, –O, –OH), freestanding films are prepared and tested as electrodes for Zn-ion hybrid supercapacitors (ZHSC), delivering a capacity up to 77 mAh g−1 (245 mAh cm−3) at 0.5 A g−1 with a capacity retention of 87% after 10,000 cycles. This promising performance in ZHSC is achieved when using Zn(CF3SO3)2 or low-cost ZnCl2 solutions. Furthermore, HE MXene films can be used as a negative electrode for Li-ion batteries with a capacity up to 126 mAh g−1 (400 mAh cm−3) at 0.01 A g−1. This report sheds light on the use of a new class of MXene films for various charge storage applications.

The MAB phases are a family of layered ternary transition metal borides, with atomically laminated crystal structures comprised of transition metal boride (M-B) layers interleaved by single, or double, Al (A) layers. Herein, density functional theory is implemented to evaluate the thermodynamic stability of disordered (Mn1-xCrx)2AlB2, and disordered and ordered (Mn1-xCrx)3AlB4 quaternaries. The (Mn1-xCrx)2AlB2 solid solutions were synthesized over the entire range of substitution. A (Mn1-xCrx)3AlB4 solid solution was produced, on the base of Cr3AlB4, to form (Mn0.33Cr0.66)3AlB4. Powder X-ray diffraction shows lattice parameter shifts and unit cell expansions indicative of successful solid solution formations.

Human-like robotic sensing aims at extracting and processing complicated environmental information via multisensory integration and interaction. Tan et al. report an artificial spiking multisensory neural network that integrates five primary senses and mimics the crossmodal perception of biological brains.

MXene-based aqueous symmetric supercapacitors (SSCs) are attractive due to their good rate performances and green nature. However, it remains a challenge to reach voltages much over 1.2 V, which significantly diminishes their energy density. Herein, we report on Mo1.33CTz MXene-based SSCs possessing high voltages in a 19.5 M LiCl electrolyte. Benefiting from the vacancy-rich structure and high stable potential window of Mo1.33CTz, the obtained SSCs deliver a maximum energy density of >38.2 mWh cm−3 at a power density of 196.6 mW cm−3 under an operating voltage of 1.4 V, along with excellent rate performance and impressive cycling stability. This highly concentrated LiCl electrolyte is also applicable to Ti3C2Tz, the most widely studied MXene, achieving a maximum energy density of >41.3 mWh cm−3 at a power density of 165.2 mW cm−3 with an operating voltage of 1.8 V. The drop in energy density with increasing power in the Ti3C2Tz cells was steeper than for the Mo-based cells. This work provides a roadmap to develop superior SSCs with high voltages and high energy densities.

Significant efforts have been dedicated to developing Ti3C2Tz‐based MXene aqueous supercapacitors (SCs) with improved energy and power densities. Notably less research has been devoted to an equally important characteristic of aqueous SCs, viz. self‐discharge (SD). The SD rates are rarely reported despite their crucial importance from a practical point of view. Herein, the SD rates in four different aqueous electrolytes: H2SO4, KOH, LiCl, and LiBr in Ti3C2Tz‐based aqueous SCs are compared. For the latter two, the SD rates vary as a function of salt concentration in the electrolytes with higher LiCl or LiBr concentrations having the lowest SD rates, viz. 78.3% and 81.5% in 14 m LiCl and LiBr, respectively, after 10 h. Further, the influence of dissolved oxygen and the purities of the starting powders are examined, and it is concluded that parasitic reactions, including oxygen, are responsible for the SD.

Designing artificial somatosensory systems to efficiently emulate biological tactile information sensing, coding, and processing remains a challenge. Here, the authors demonstrate a tactile sensory system based on optoelectronic spiking afferent nerves with both coding and learning capabilities.

We report the synthesis of eight new members of the i-MAX family, of the formula (Mo2/3RE1/3)2GaC, where RE = Gd, Tb, Dy, Ho, Er, Tm, Lu, and Yb, the latter not previously incorporated in a MAX phase. The structure and composition of powder samples were investigated by X-ray diffraction, scanning transmission electron microscopy, and energy dispersive X-ray analysis combined with scanning electron microscopy. All phases showed evidence of an orthorhombic (Cmcm) structure, and the phases based on Er and Yb also crystallized in a monoclinic (C2/c) arrangement. The chemical order of the magnetic elements suggests interesting magnetic characteristics, with a high tuning potential through the range of attainable lanthanide elements.

The thickness dependence and long-term stability of the magnetic properties of epitaxial (Cr0.5Mn0.5)2GaC MAX phase films on MgO (111) were investigated. For 12.5- to 156-nm-thick films, which corresponds to 10–125 c-axis unit cells, samples were found to be phase pure with negligible c-axis lattice strain of less than 10−4 nm even for the thinnest films. No influence of the interface layers on the magnetic anisotropy, the magnetization or the para- to ferromagnetic phase transition was observed. All samples remained stable for more than one year in ambient conditions.

Abstract Enhancing both the energy storage and power capabilities of electrochemical capacitors remains a challenge. Herein, Ti3C2Tz MXene is mixed with MoO3 nanobelts in various mass ratios and the mixture is used to vacuum filter binder free, open, flexible, and free‐standing films. The conductive Ti3C2Tz flakes bridge the nanobelts, facilitating electron transfer; the randomly oriented, and interconnected, MoO3 nanobelts, in turn, prevent the restacking of the Ti3C2Tz nanosheets. Benefitting from these advantages, a MoO3/Ti3C2Tz film with a 8:2 mass ratio exhibits high gravimetric/volumetric capacities with good cyclability, namely, 837 C g−1 and 1836 C cm−3 at 1 A g−1 for an ≈ 10 µm thick film; and 767 C g−1 and 1664 C cm−3 at 1 A g−1 for ≈ 50 µm thick film. To further increase the energy density, hybrid capacitors are fabricated with MoO3/Ti3C2Tz films as the negative electrodes and nitrogen‐doped activated carbon as the positive electrodes. This device delivers maximum gravimetric/volumetric energy densities of 31.2 Wh kg−1 and 39.2 Wh L−1, respectively. The cycling stability of 94.2% retention ratio after 10 000 continuous charge/discharge cycles is also noteworthy. The high energy density achieved in this work can pave the way for practical applications of MXene‐containing materials in energy storage devices.

We study the origin of layer decoupling in ordered multilayer graphene grown by high temperature sublimation on C-face 4H-SiC. The mid-infrared optical Hall effect technique is used to determine the magnetic field dependence of the inter-Landau level transition energies and their optical polarization selection rules, which unambiguously show that the multilayer graphene consists of electronically decoupled layers. Transmission electron microscopy reveals no out-of-plane rotational disorder between layers in the stack, which is in contrast to what is typically observed for C-face graphene grown by low temperature sublimation. It is found that the multilayer graphene maintains AB-stacking order with increased interlayer spacing by 2.4%–8.4% as compared to highly oriented pyrolytic graphite. Electron energy loss spectroscopy mapping reveals Si atoms trapped in between layers, which are proposed to be the cause for the observed increased interlayer spacing leading to layer decoupling. Based on our results, we propose a defect-driven growth evolution mechanism for multilayer graphene on C-face SiC via high temperature sublimation.

The first Fe-based MAX phase is realized by solid-state substitution reaction of an Fe/Au/Mo2GaC thin-film diffusion couple, as determined by X-ray diffraction and scanning transmission electron microscopy. Chemical analysis together with elemental mapping reveals that as much as 50 at.% Fe on the A site can be obtained by thermally induced Au and Fe substitution for Ga atomic layers in Mo2GaC. One-sixth of the original Ga is also replaced by Au atoms. When annealing Mo2GaC thin films covered with Fe only, the Mo2GaC phase remains intact, that is, Au acts as a catalyst for the substitution reaction. IMPACT STATEMENT The first direct evidence showing Fe-containing MAX phase, Mo2AC, with Fe ∼50 at.% on the A sites is presented, synthesized by thermally induced Fe and Au substitution reaction catalyzed by Au.

Vacancies in 2D materials can influence their properties, however controlling their formation remains a challenge. Here the authors show that selective etching of a 3D laminate with in-plane chemical ordering results in formation of MXenes with ordered divacancies, as well as elevated conductance and supercapacitance.

The data presented in this paper are related to the research article entitled “Theoretical stability and materials synthesis of a chemically ordered MAX phase, Mo2ScAlC2, and its two-dimensional derivate Mo2ScC” (Meshkian et al. 2017) [1]. This paper describes theoretical phase stability calculations of the MAX phase alloy MoxSc3-xAlC2 (x=0, 1, 2, 3), including chemical disorder and out-of-plane order of Mo and Sc along with related phonon dispersion and Bader charges, and Rietveld refinement of Mo2ScAlC2. The data is made publicly available to enable critical or extended analyzes.

Herein, we investigate the influence of powder metallurgical manufactured Ti0.5Al0.5 cathode grain size (45-150 μm) on the properties of a DC arc discharge, for N2 pressures in the range 10-5 Torr (base pressure) up to 3x10-2 Torr. Intermetallic TiAl cathodes are also studied. The arc plasma is characterized with respect to ion composition, ion charge state, and ion energy, and is found to change with pressure, independent on choice of cathode. Scanning electron microscopy, X-ray diffraction, and Energy-dispersive X-ray spectroscopy of the cathode surfaces and the concurrently deposited films are used for exploring the correlation between cathode-, plasma-, and film composition. The plasma has a dominating Al ion content at elevated pressures, while the film composition is consistent with the cathode composition, independent on cathode grain size. Cross-sections of the used cathodes are studied, and presence of a converted layer, up to 10 μm, is shown, with an improved intermixing of the elements on the cathode surface. This layer is primarily explained by condensation of cathode material from the melting and splashes accompanying the arc spot movement, as well as generated plasma ions being redeposited upon returning to the cathode. The overall lack of dependence on grain size is likely due to similar physical properties of Ti, Al and TiAl grains, as well as the formation of a converted layer. The presented findings are of importance for large scale manufacturing and usage of Ti-Al cathodes in industrial processes.

Herein, we present stable and reproducible arc plasma generation from a TiB2 cathode. The process development contains three complimentary features: Use of a Mo cylinder around the TiB2 cathode improves arc ignition and stabilizes the process by keeping the arc spot at the cathode surface. The evolution of the cathode surface during erosion and the process stability is further improved by addition of 1wt% carbon in the cathode, with no resulting change in plasma characteristics (ion energy, ion charge states, macroparticles). Finally, an increased plasma density through use of a separate anode provides the last key point, which together with the other two contributes to highly controlled plasma generation from TiB2 using DC vacuum arc, and complete utilization of the cathode material. The combined results provide a novel and efficient route for synthesis of metal borides.

We have deposited epitaxial thin films of the inverse perovskite Mn _3 GaC using magnetron sputtering from elemental targets. Two substrates were used, MgO (111) and (100), resulting in corresponding orientation of the Mn _3 GaC thin films. Both samples displayed magnetic properties consistent with an AFM to FM transition at ∼170 K and a Curie temperature around 265 K, evaluated with vibrating sample magnetometry (in-plane measurements). These two ground states are further supported by first principles calculations. Based on that the two orientations of Mn _3 GaC display very similar magnetic properties, it can be concluded that shape anisotropy dominates over the material’s easy axis.

The magnetic properties of the new phase (Cr0.5Mn0.5)2AuC are compared to the known MAX-phase (Cr0.5Mn0.5)2GaC, where the former was synthesized by thermally induced substitution reaction of Au for Ga in (Cr0.5Mn0.5)2GaC. The reaction introduced a lattice expansion of ∼3% along the c-axis, an enhancement of the coercive field from 30 mT to 140 mT, and a reduction of the Curie temperature and the saturation magnetization. Still, (Cr0.5Mn0.5)2AuC displays similar features in the magnetic field- and temperature-dependent magnetization curves as previously reported magnetic MAX phases, e.g., (Cr0.5Mn0.5)2GaC and (Mo0.5Mn0.5)2GaC. The work suggests a pathway for tuning the magnetic properties of MAX phases.