Amorphous Counterparts Research Articles

How Amorphous Nanomaterials Enhanced Electrocatalytic, SERS, and Mechanical Properties.

There is ever-growing research interest in nanomaterials because of the unique properties that emerge on the nanometer scale. While crystalline nanomaterials have received a surge of attention for exhibiting state-of-the-art properties in various fields, their amorphous counterparts have also attracted attention in recent years owing to their unique structural features that crystalline materials lack. In short, amorphous nanomaterials only have short-range order at the atomic scale, and their atomic packing lacks long-range periodic arrangement, in which the coordinatively unsaturated environment, isotropic atomic structure, and modulated electron state all contribute to their outstanding performance in various applications. Given their intriguing characteristics, we herein present a series of representative works to elaborate on the structural advantages of amorphous nanomaterials as well as their enhanced electrocatalytic, surface-enhanced Raman scattering (SERS), and mechanical properties, thereby elucidating the underlying structure-function relationship. We hope that this proposed relationship will be universally applicable, thus encouraging future work in the design of amorphous materials that show promising performance in a wide range of fields.

Crystalline versus Amorphous: High-Performance Hafnium Phosphonate Framework for the Separation of Uranium and Transuranium Elements.

Metal phosphonate frameworks (MPFs) consisting of tetravalent metal ions and aryl-phosphonate ligands feature a large affinity for actinides and excellent stabilities in harsh aqueous environments. However, it remains elusive how the crystallinity of MPFs influences their performance in actinide separation. To this end, we prepared a new category of porous, ultrastable MPF with different crystallinities for uranyl and transuranium separation. The results demonstrated that crystalline MPF was generally a better adsorbent for uranyl than the amorphous counterpart and ranked as the top-performing one for uranyl and plutonium in strong acidic solutions. A plausible uranyl sequestration mechanism was unveiled by using powder X-ray diffraction in tandem with vibrational spectroscopy, thermogravimetry, and elemental analysis.

The Difference in Performance and Compatibility between Crystalline and Amorphous Fillers in Mixed Matrix Membranes for Gas Separation (MMMs).

An increasing number of high-performing gas separation membranes is reported almost on a daily basis, yet only a few of them have reached commercialisation while the rest are still considered pure research outcomes. This is often attributable to a rapid change in the performance of these separation systems over a relatively short time. A common approach to address this issue is the development of mixed matrix membranes (MMMs). These hybrid systems typically utilise either crystalline or amorphous additives, so-called fillers, which are incorporated into polymeric membranes at different loadings, with the aim to improve and stabilise the final gas separation performance. After a general introduction to the most relevant models to describe the transport properties in MMMs, this review intends to investigate and discuss the main advantages and disadvantages derived from the inclusion of fillers of different morphologies. Particular emphasis will be given to the study of the compatibility at the interface between the filler and the matrix created by the two different classes of additives, the inorganic and crystalline fillers vs. their organic and amorphous counterparts. It will conclude with a brief summary of the main findings.

Survival of Zirconium-Based Metal-Organic Framework Crystallinity at Extreme Pressures.

Recent research on metal-organic frameworks (MOFs) has shown a shift from considering only the crystalline high-porosity phases to exploring their amorphous counterparts. Applying pressure to a crystalline MOF is a common method of amorphization, as MOFs contain large void spaces that can collapse, reducing the accessible surface area. This can be either a desired change or indeed an unwanted side effect of the application of pressure. In either case, understanding the MOF's pressure response is extremely important. Three such MOFs with varying pore sizes (UiO-66, MOF-808, and NU-1000) were investigated using in situ high-pressure X-ray diffraction and Raman spectroscopy. Partial crystallinity was observed in all three MOFs above 10 GPa, along with some recovery of crystallinity on return to ambient conditions if the frameworks were not compressed above thresholds of 13.3, 14.2, and 12.3 GPa for UiO-66, MOF-808, and NU-1000, respectively. This threshold was marked by an unexpected increase in one or more lattice parameters with pressure in all MOFs. Comparison of compressibility between MOFs suggests penetration of the pressure-transmitting oil into MOF-808 and NU-1000. The survival of some crystallinity above 10 GPa in all of these MOFs despite their differing pore sizes and extents of oil penetration demonstrates the importance of high-pressure characterization of known structures.

Orally delivered 2D covalent organic frameworks releasing kynurenine generate anti-inflammatory T cell responses in collagen induced arthritis mouse model

Covalent organic framework (COF) crystalline biomaterials have great potential for drug delivery since they can load large amounts of small molecules (e.g. metabolites) and release them in a controlled manner, as compared to their amorphous counterparts. Herein, we screened different metabolites for their ability to modulate T cell responses in vitro and identified Kynurenine (KyH) as a key metabolite that not only decreases frequency of pro-inflammatory RORgt + T cells but also supports frequency of anti-inflammatory GATA3+ T cells. Moreover, we developed a methodology to generate imine-based TAPB-PDA COF at room temperature and loaded these COFs with KyH. KyH loaded COFs (COF-KyH) were able to then release KyH in a controlled manner for 5 days in vitro. Notably, COF-KyH when delivered orally in mice induced with collagen-induced rheumatoid arthritis (CIA) were able to increase frequency of anti-inflammatory GATA3+CD8+ T cells in the lymph nodes and decrease antibody titers in the serum as compared to the controls. Overall, these data demonstrate that COFs can be an excellent drug delivery vehicle for delivering immune modulating small molecule metabolites.

Superlattice-shelled nanocrystalline core structural design for highly sensitive GMI sensors

Giant magnetic impendence (GMI) sensors are known as a significant pillar of modern technology, and has many applications in smart society such as automation, navigation and bioengineering. Developing high-sensitive GMI sensors operating under extremely weak magnetic fields is highly desirable yet challenging. Here, we proposed superlattice-shelled nanocrystalline core structural design in the cobalt-based amorphous sensor-core microwires for the highly sensitive GMI sensors. Continuous Co-based amorphous microwires with a length up to thousands of meters and uniform diameter is first fabricated by a scalable modified Taylor–Ulitovsky method and then processed by the picosecond lasering heat treatment. As a result, the microwire exhibits a unique nanostructure consisting of ultrafine nanocrystalline cores surround by the thermal-stable Cr-rich superlattice shell, and hence circumferential magnetic domains of the higher density and intensity. The GMI sensors made from nanostructured Co-based microwires show a sensitivity up to 1743 mV/Oe, the maximum GMI ratio up to 78%, increasing the performance by up to twice and nine times respectively over the GMI sensor made from the amorphous counterpart, and a wide linear range of ± 70000 nT. The correlation between the microstructure, magnetic domain structure and GMI performance is also established and discussed in the nanostructured Co-based microwires. Furthermore, we demonstrate the successful application of the highly sensitive GMI sensor in geomagnetic communication to detect underground energy transmission metal pipes with a detection resolution down to pT-level weak magnetic fields.

Heterogeneity of microstructures in a Cu–Zr based amorphous alloy composite reinforced by crystalline phases

Amorphous alloy composites (AACs) comprising reinforcing crystalline phases exhibit far better mechanical properties than their base amorphous alloy counterparts, and Cu–Zr based alloys consisting of B2 phase particles embedded in an amorphous matrix are well-researched AACs in this respect. Traditionally, the B2 particles in Cu–Zr based AACs may appear to be homogeneously crystalline (without any amorphous phase inside), the glassy matrix homogeneously amorphous, and their interfaces atomically sharp. Yet, such a picture would pose difficulties in understanding how crystallization can happen in the glassy matrix, since the crystallized product is denser than but iso-stoichiometric with the matrix. The present work provides insights into this puzzle, by using electron microscopy, nanoindentation and molecular dynamics (MD) simulations to investigate the structures and mechanical properties of the crystalline and amorphous phases, and their interfaces in a Cu62Zr34.5Al3Nb0.5 AAC. Surprisingly, in this AAC, the superficially crystalline particles with tens to hundreds of microns large are found to be heterogeneous at the sub-micron scale, comprising nano-crystallites embedded in a glassy matrix, and the amorphous phase outside also exhibits a gradient in free volume content towards the interface. Smaller particles containing only B2 nano-crystallites are found to be softer than the amorphous matrix, while larger particles are harder than the amorphous phase due to martensitic transformation into the B19’ phase. MD simulations indicate that the B2 phase is marginally more stable than the glassy state, and on crystallization the densification leads to free-volume generation in the surrounding glassy matrix as observed experimentally. Mechanics analysis indicates that the strain energy in the glassy matrix associated with free-volume generation scales with the volume of the crystallization, as would be the crystallization energy itself. Hence, crystallization in the AAC leading to a two-phase structure is a spontaneous but kinetically limiting process arising from the net energy difference between the crystallization energy and free-volume energy produced in the glassy matrix. This work provides a detailed understanding of the heterogeneity in the microstructures in Cu–Zr based AACs, to shed light on the crystallization of the iso-stoichiometric B2 phase from the amorphous phase.

Capping-layer-mediated lattice mismatch and redox reaction in SrTiO3-based bilayers

It is well known that the traditional two-dimensional electron system (2DES) hosted by the SrTiO3 substrate can exhibit diverse electronic states by modifying the capping layer in heterostructures. However, such capping layer engineering is less studied in the SrTiO3-layer-carried 2DES (or bilayer 2DES), which is different from the traditional one on transport properties but more applicable to the thin-film devices. Here, several SrTiO3 bilayers are fabricated by growing various crystalline and amorphous oxide capping layers on the epitaxial SrTiO3 layers. For the crystalline bilayer 2DES, the monotonical reduction on the interfacial conductance, as well as carrier mobility, is recorded on increasing the lattice mismatch between the capping layers and epitaxial SrTiO3 layer. The mobility edge raised by the interfacial disorders is highlighted in the crystalline bilayer 2DES. On the other hand, when increasing the concentration of Al with high oxygen affinity in the capping layer, the amorphous bilayer 2DES becomes more conductive accompanied by the enhanced carrier mobility but almost constant carrier density. This observation cannot be explained by the simple redox-reaction model, and the interfacial charge screening and band bending need to be considered. Moreover, when the capping oxide layers have the same chemical composition but with different forms, the crystalline 2DES with a large lattice mismatch is more insulating than its amorphous counterpart, and vice versa. Our results shed some light on understanding the different dominant role in forming the bilayer 2DES using crystalline and amorphous oxide capping layer, which may be applicable in designing other functional oxide interfaces.

Realigning the melon chains in carbon nitride by rubidium ions to promote photo-reductive activities for hydrogen evolution and environmental remediation

The photocatalytic efficiency of polymeric carbon nitride (PCN) suffers from unsatisfactory charge separation because of its amorphous structure. Herein, we report a simple bottom-up method to synthesize a novel structure of rubidium ion inserted PCN (Rb-PCN), which involves the regular alignment of melon chains to endow a crystalline feature in PCN. The insertion of Rb+ decreased not only the N p electrons in the heptazine ring but also the plane angle of the heptazine motifs in the melon chain, which promoted the long-range periodicity and crystallinity of carbon nitride. This structurally rearranged crystalline Rb-PCN demonstrated considerably enhanced separation of charge carriers, resulting in six-fold higher photocatalytic hydrogen evolution activity than its amorphous counterpart. Furthermore, the photoexcited electrons can be efficiently trapped by O2 to generate H2O2, which facilitates the production of reactive oxygen species to inactivate bacteria and degrade organic pollutants, showing great potential for use in both energy and environmental applications.

Localized Bound Multiexcitons in Engineered Quasi-2D Perovskites Grains at Room Temperature for Efficient Lasers.

Reducing the excitation threshold to minimize the Joule heating is critical for the realization of perovskite laser diodes. Although bound excitons are promising for low threshold laser, how to generate them at room temperature for laser applications is still unclear in quasi-2D perovskite-based devices. In this work, via engineering quasi-2D perovskite PEA2 (CH3 NH3 )n -1 Pbn Br3 n +1 microscopic grains by the anti-solvent method, room-temperature multiexciton radiative recombination is successfully demonstrated at a remarkably low pump density of 0.97 µJ cm-2 , which is only one-fourth of that required in 2D CdSe nanosheets. In addition, the well-defined translational momentum in quasi-2D perovskite grains can restrict the Auger recombination which is detrimental to radiative emission. Furthermore, the quasi-2D perovskite grains are favorable for increasing binding energies of excitons and biexcitons and so as the related radiative recombination. Consequently, the prepared <n= 8> phase quasi-2D perovskite film renders a threshold of room-temperature stimulated emission as low as 13.7 µJ cm-2 , reduced by 58.6% relative to the amorphous counterpart with larger grains. The findings in this work are expected to facilitate the development of solution-processable perovskite multiexcitonic laser diodes.

Effective and selective electrocatalytic nitrate reduction to ammonia on urchin-like and defect-enriched titanium oxide microparticles

This work reported a facile approach to surface oxygen vacancy (OV)-enriched urchin-like TiO2 microparticles (U-TiO2), which were highly effective and durable in catalyzing selective nitrate reduction to ammonia (NO3RR). Specifically, the U-TiO2 delivered a mass activity of 1.15 min−1 mg−1catalyst, a low yield of toxic NO2−-N intermediate (≤0.4 mg/L) and an exceptional high NH3-N selectivity of 98.1% in treating 22.5 mg/L of NO3−-N under a potential of -0.60 V vs. RHE, outperforming most of the reported oxide-based catalysts. When comparing the performance of U-TiO2 with that of the solid amorphous TiO2 counterpart (A-TiO2) that had close particle size but more OV on surfaces, we identified that the OV was the reactive sites, but rather than its content, the NO3RR kinetics were primarily limited by the electron and mass transfer at U-TiO2/water interfaces. Accordingly, the superior performance of U-TiO2 to A-TiO2 could be ascribed to the hierarchical urchin-like structure in U-TiO2. The in-situ DEMS test revealed that the NO3RR on U-TiO2 followed a pathway of *NO3− → *NO2−→ *NO → *N → *NH → *NH2 → *NH3. We also demonstrated that the U-TiO2 could keep its robust performance under a wide NO3−-N concentration range and in the presence of some co-existing ions (such as Ca2+, Cl−, Mg2+). However, the presence of humic acid and CO32− in water slowed down the NO3RR on U-TiO2. This work provides a more fundamental insight into the OV-driven NO3RR process on TiO2, which should benefit for the development of efficient TiO2-based catalysts.

Cation Exchange between CdSe Nanocrystals and Pd2+ Cations in Different Solvent Environments toward Phase-Dependent Ethanol Oxidation Electrocatalysis.

The cation-exchange strategy has shown great potential to create a large variety of inorganic nanostructures. We herein report the cation-exchange reactions between CdSe nanocrystals and Pd2+ cations in different solvent environments and identify three features not sufficiently noticed before: (i) the exchange between Cd2+ and Pd2+ cations could be fully achieved in both aqueous and organic solvents and is also independent of its parent CdSe crystal structures; (ii) the exchange between Cd2+ and Pd2+ cations in aqueous solvent results in amorphous Pd-Se exchanged products, while in organic solvent, it leads to a cubic Pd17Se15 phase; and (iii) the exchanged Pd17Se15 product exhibits better electrocatalysis for ethanol oxidation reaction in an alkaline medium relative to its amorphous counterpart and the commercial Pd/C catalyst.

Vanadium Oxides with Amorphous-Crystalline Heterointerface Network for Aqueous Zinc-Ion Batteries.

Rechargeable aqueous Zn-VOx batteries are attracting attention in large scale energy storage applications. Yet, the sluggish Zn2+ diffusion kinetics and ambiguous structure-property relationship are always challenging to fulfil the great potential of the batteries. Here we electrodeposit vanadium oxide nanobelts (VO-E) with highly disordered structure. The electrode achieves high capacities (e.g., ≈5 mAh cm-2 , 516 mAh g-1 ), good rate and cycling performances. Detailed structure analysis indicates VO-E is composed of integrated amorphous-crystalline nanoscale domains, forming an efficient heterointerface network in the bulk electrode, which accounts for the good electrochemical properties. Theoretical calculations indicate that the amorphous-crystalline heterostructure exhibits the favorable cation adsorption and lower ion diffusion energy barriers compared to the amorphous and crystalline counterparts, thus accelerating charge carrier mobility and electrochemical activity of the electrode.

Vanadium Oxides with Amorphous‐Crystalline Heterointerface Network for Aqueous Zinc‐Ion Batteries

AbstractRechargeable aqueous Zn‐VOxbatteries are attracting attention in large scale energy storage applications. Yet, the sluggish Zn2+diffusion kinetics and ambiguous structure–property relationship are always challenging to fulfil the great potential of the batteries. Here we electrodeposit vanadium oxide nanobelts (VO‐E) with highly disordered structure. The electrode achieves high capacities (e.g., ≈5 mAh cm−2, 516 mAh g−1), good rate and cycling performances. Detailed structure analysis indicates VO‐E is composed of integrated amorphous‐crystalline nanoscale domains, forming an efficient heterointerface network in the bulk electrode, which accounts for the good electrochemical properties. Theoretical calculations indicate that the amorphous‐crystalline heterostructure exhibits the favorable cation adsorption and lower ion diffusion energy barriers compared to the amorphous and crystalline counterparts, thus accelerating charge carrier mobility and electrochemical activity of the electrode.

Ferromagnetism of Nanometer Thick Sputtered Fe3GeTe2 Films in the Absence of Two-Dimensional Crystalline Order: Implications for Spintronics Applications

The discovery of ferromagnetism in two-dimensional (2D) monolayers has stimulated growing research interest in both spintronics and material science. However, these 2D ferromagnetic layers are mainly prepared through an incompatible approach for large-scale fabrication and integration, and moreover, a fundamental question of whether the observed ferromagnetism actually correlates with the 2D crystalline order has not been explored. Here, we choose a typical 2D ferromagnetic material, Fe3GeTe2, to address these two issues by investigating its ferromagnetism in an amorphous state. We have fabricated nanometer thick amorphous Fe3GeTe2 films approaching the monolayer thickness limit of crystallized Fe3GeTe2 (0.8 nm) through magnetron sputtering. Compared to crystallized Fe3GeTe2, we found that the basic ferromagnetic attributes, such as the Curie temperature which directly reflects magnetic exchange interactions and local anisotropic energy, do not change significantly in the amorphous states. This is attributed to the short-range atomic order, as confirmed by valence state analysis, being almost the same for both phases. The persistence of ferromagnetism in the ultrathin amorphous counterpart has also been confirmed through magnetoresistance measurements, where two unconventional switching dips arising from electrical transport within domain walls are clearly observed in the amorphous Fe3GeTe2 single layer. These results indicate that the long-range ferromagnetic order of crystallized Fe3GeTe2 may not correlate to the 2D crystalline order, and the corresponding ferromagnetic attributes can be utilized in an amorphous state which suits large-scale fabrication in a semiconductor technology-compatible manner for spintronics applications.

Production of Bi-Compartmental Tablets by FDM 3D Printing for the Withdrawal of Diazepam

Diazepam (DZP) is a long-acting benzodiazepine to treat anxiety or acute alcohol withdrawal. Although this class of drugs should be taken for a short period of time, many patients take them for longer than recommended, which has been linked to an increased risk of dementia and dependence. The present work aimed at using the dual-nozzle system of fused deposition modeling (FDM) 3D printers to prepare tablets with gradual doses of DZP with constant mass and size. Placebo and DZP-loaded filaments were prepared by hot-melt extrusion and used to print the bi-compartmental tablets. Thermal processing allowed the conversion of crystalline DZP to its amorphous counterpart. Tablets with different DZP contents were effectively printed with a mass, thickness and diameter average of 111.6 mg, 3.1 mm, and 6.4 mm, respectively. Microscopic data showed good adhesion between the different layers in the printed tablets. The desired drug contents were successfully achieved and were within the acceptance criteria (European Pharmacopeia). The combination of a placebo and drug-loaded extrudates proved to be beneficial in the production of tablets by FDM for patients in need of drug withdrawal.

A Comparison of Photodeposited RuOx for Alkaline Water Electrolysis

The storage of renewable energy is a pressing challenge to overcome in the transition toward a power grid based on plentiful, yet intermittent energy supplies. The renewables-driven electrolysis of water to form hydrogen fuel is an attractive avenue, but requires better oxygen-evolution reaction (OER) catalysts to be feasible at scale. RuO2 is touted as one of the superior OER catalysts but only under acidic conditions; RuO2 electrocatalysts suffer from poor stability under alkaline conditions. In this work, we evaluate three photodeposited RuOx OER electrocatalysts, all prepared via a scalable photodeposition method. Based on electrochemical and spectroscopic studies (X-ray photoelectron spectroscopy and X-ray absorption spectroscopy), our main findings are that nanocrystalline RuOx catalysts outperform their amorphous counterpart and are more stable under alkaline (0.1 M KOH) conditions. This works thus lifts a major hurdle toward the use of RuOx for alkaline water electrolysis.

Highly Crystalline Rubrene Light‐Emitting Diodes with Epitaxial Growth

AbstractConventional organic optoelectronic devices suffer from low carrier mobility limited by the static and dynamic disorder. Organic crystals with long‐range order can circumvent the effects of disorder and significantly improve the charge transport. While highly ordered organic crystals offer the desirable electronic coupling strength and charge transport, their integration into large‐area optoelectronic devices remains a challenge. Here, monolithic integrated triclinic crystal rubrene light‐emitting diodes (LEDs) are presented using epitaxial growth with functional additives being engineered into the films. Superior charge transport, excellent operational and long‐term stability in these light‐emitting devices are demonstrated. By comparing two rubrene‐based LEDs, one made from amorphous and one from crystalline rubrene layers, their exciton dynamics are estimated using comprehensive transient electroluminescence simulation. The crystalline LEDs show high triplet‐triplet annihilation (TTA) rate constant similar to TTA rate constant of triclinic single crystals determined by optical spectroscopy. At the same time, the crystalline phase enhances drastically the singlet‐fission and bimolecular annihilation rates, which reduces the overall performance of the LED compared to its amorphous counterpart. Finally, an outlook on the potential applications of rubrene and/or its derivatives crystalline films are provided for enhancing the performance of organic and hybrid optoelectronic devices.

Order-disorder engineering of RuO2 nanosheets towards pH-universal oxygen evolution.

Ru-based electrocatalysts are considered promising anode catalysts towards water electrolysis due to their impressive activity under acidic conditions. Yet, caused by the collapse of the local crystalline domains and concurrent leaching of Ru species during the OER process, durability against structural degradation remains poor. Herein, we present an order-disorder structure optimization strategy, based on RuO2 nanosheets with well-defined amorphous-crystalline boundaries supported on carbon cloth (a/c-RuO2/CC), to effectively catalyze water oxidation, especially in the case of an acidic medium. Specifically, the as-prepared a/c-RuO2/CC sample has achieved a lower overpotential of 150 mV at 10 mA cm-2, a smaller Tafel slope of 47 mV dec-1, and a significantly higher durability with suppressed dissolution of Ru, with regard to its crystalline (c-RuO2/CC) and amorphous (a-RuO2/CC) counterparts. Computational simulations combined with experimental characterizations uncover that the construction of the structurally ordered-disordered boundary enables a weakened Ru-O covalency with regard to the ordered counterpart, which suppresses the leaching of active Ru species from the crystalline phase, thus enhances stability. An upshift of the d-band center in a/c-RuO2/CC relative to a-RuO2/CC reduces the energy barrier of the potential-determining step (*O → *OOH), thereby dramatically boosting activity.

In-situ Neutron Reflectometry to Determine Ge Self-Diffusivities and Activation Energy of Diffusion in Amorphous Ge0.8Si0.2

Amorphous Ge-Si solid solutions are an interesting class of materials from the fundamental as well as the technological point of view. Self-diffusion of the constituents is an important process because of the inherent metastability. While self-diffusion was already examined in crystalline GexSi1-x (0 &lt; x &lt;1) this is not the case for the amorphous counterparts. This work reports on Ge self-diffusivities obtained from insitu neutron reflectometry measurements during isothermal annealing of ion-beam sputter-deposited amorphous Ge0.8Si0.2 films. The diffusivities are modified peculiarly fast with annealing time by a maximum factor of two due to structural relaxation. The diffusivities in the relaxed state are lower (higher) than in amorphous germanium (silicon). They follow the Arrhenius law and show an activation energy of (2.06 ± 0.1) eV, which equals that of amorphous germanium, but differs from that of amorphous silicon. Thus, it is concluded that the diffusion mechanism of Ge in amorphous Ge0.8Si0.2 and Ge are similar, despite of the presence of dispersed 20 at.% of Si.