Crystal Surface Research Articles

Sub-2.5 nm monodisperse Mo2C nanoparticles on N-doped carbon: The facet engineering for boosting electrochemical hydrogen evolution

Molybdenum carbide materials have demonstrated remarkable potential in catalyzing the hydrogen evolution reaction (HER). However, further modulation of their performance through simultaneously engineering the size and surface crystal facets remains challenging. Herein, we report the successful fabrication of N-doped carbon-supported monodisperse Mo2C nanoparticles with a size of ∼2.06 nm, exhibiting co-exposed (101)/(102) facets-heterojunction, derived from annealing glycine and ammonium molybdate tetrahydrate. The optimized Mo2C/NC-Amt catalyst exhibits a low overpotentials of 128 mV to achieve the current density of 10 mA cm−2 and a small Tafel slope of 72 mV dec−1 under alkaline solution. By changing the molybdate precursor, the phase and crystal facet composition of molybdenum carbide can be effectively tuned, which provides a good platform for studying their structure-activity in HER. The theoretical calculations reveal the synergistic effect of (101)/(102) facets-heterojunction accelerates electron transfer and regulates the d band center of Mo2C, reducing the reaction barriers of intermediates in the HER process, thus significantly boosting reaction activity. This work proposes a novel insight into the rational fabrication of efficient HER catalysts through facet engineering toward heterojunction construction under the 2.5 nm region.

The role of sulfate in the hydrothermal replacement of aragonite single crystals by calcite

Aragonite (CaCO3) is a stable calcium carbonate phase under high pressure conditions. However, its formation in (sub)surface environments, where calcite is the stable polymorph, is widespread. Regardless of its origin, aragonite is expected to undergo transformation into calcite under moderate pressures and temperatures. However, this transformation does not always take place, which results in the presence of abundant aragonitic relics in the geological record. Traditionally, this preservation has been explained by the presence of chemical inhibitors that prevent the conversion of aragonite to calcite. While it is widely accepted that magnesium (Mg) plays a key role in the polymorphic selection of CaCO3, the influence of other ions has also been suggested. This work evaluates the effect that different concentrations of sulfate (SO42−) in the fluid has on the progress of the aragonite-to-calcite transformation at 220 °C. Our results show that, upon reaction with deionized water or sulfate-poor solutions ([SO42−]aq < 0.1 mM), aragonite single crystals are extensively replaced by calcite aggregates (crystal size > 15 µm) through an interface coupled dissolution-precipitation reaction. The replacement starts at the aragonite crystal surfaces and advances inwards thanks to the development of an extensive network of fractures. Contrarily, when the solution bears higher concentrations of sulfate ([SO42−]aq > 0.1 mM), only a thin layer of smaller crystals of calcite (< 10 µm) form on the aragonite substrates, without any further transformation taking place. We interpret that these smaller crystals exert too little crystallization pressure and fail to promote the development of a network of fractures. In the absence of this network, the aragonite-calcite transformation cannot take place. The transformation does not occur neither when the experiments are conducted with deionized water and fragments of gypsum or anhydrite together with the aragonite grains. The results of this study shed light on the influence of dissolved sulfate in the kinetics of the fluid-driven transformation of aragonite into calcite. These results are useful to understand the preservation of aragonite in a variety of current geological settings and provide valuable insights for better understanding the diagenesis of sedimentary carbonates.

Negative reflection and total internal reflection at the internal surface of lithium niobate crystal

In this paper we analytically find out the expression for the wave vector and Poynting vector in the reflection domain for negative uniaxial material. We investigate the impact of the optical axis rotation and incident angle on the wave vector and Poynting vector reflected from the internal surface of lithium niobate crystal when the light is propagating from the denser anisotropic medium to the rarer isotropic medium. We derive the Brewster angle condition and discuss the walk-off between TE and TM polarized light. We explore where the wave vector and Poynting vector are parallel after reflection. In further analysis, we look into the phase differences between ordinary and extraordinary reflected light after total internal reflection from the internal surface of lithium niobate crystal. The necessary conditions for linear polarization and circular polarization have been established. The impact of optical axis orientation is also taken into consideration. The refractive index for the isotropic material for the desired polarization response has been found as 2.18, 2.1, and 2.03 at 632 nm, 1550 nm, and 3500 nm, respectively.

Application of Multiple Scales Method to the Problem About Characteristics of the Ionic Layer Near The Surface of Lithium Niobate Crystal in a Benzoic Acid Melt

Application of Multiple Scales Method to the Problem About Characteristics of the Ionic Layer Near The Surface of Lithium Niobate Crystal in a Benzoic Acid Melt

Crystal structure, composition and valence state of cations in mixed-valence A1-xCdxMnO3 (A=Pr, La) ceramics

Abstract Complex manganites A1−xCdxMnO3 (A = Pr, La) are synthesized by solid state reaction method. X-ray diffraction, scanning electron microscopy and energy-dispersive analysis are applied to study their crystal structure, surface morphology, elemental and phase composition. X-ray photoelectron spectroscopy (XPS) methods are used to study the charge states of Pr and La cations, as well as to quantify the fractions of coexisting Mn3+ and Mn4+ ions. La3d-, La4d-, Pr4d- и Mn2p-spectra of La3+, Pr3+, Mn3+ and Mn4+ ions are calculated in the isolated–ion approximation with accounting for multiplet splitting and charge transfer effect. Good agreement with the experiment is obtained. The relative fractions of trivalent and tetravalent manganese ions in La0.45Cd0.78Mn0,9O2.86 and Pr0.50Cd0.76Mn0.86O2.88 samples are determined by fitting the Mn2p spectra by superposition of experimental spectra containing only Mn3+, and only Mn4+ ions; they were found to be 0.71Mn3+/0.29Mn4+ and 0.54Mn3+/0.46Mn4+, respectively.

Photochemical wet etching of (0 0 1) plane ß-phase Ga2O3, and its anisotropic etching behavior

The photochemical (PC) wet etching behavior of (001) plane β-phase Ga2O3(β-Ga2O3)single crystal was investigated using potassium hydroxide etchant solution under ultraviolet illumination in the temperature range of 80–95 °C. The etch rate was 1.65 nm/min at 80 °C, and increased up to 4.88 nm/min at 95 °C. The etch rate of the (001) plane β-Ga2O3shows strong temperature dependence with the activation energy of 0.798 eV. The PC wet etching characteristics of the (001) plane β-Ga2O3was compared with those of (2¯01) and (010) plane β-Ga2O3. The etch rates increased in order of the (010), (2¯01), and (001) plane, which is accordance with the increasing surface energy trend. The oval line-shaped grooves aligned along [010] direction were observed on the etched (001) plane β-Ga2O3 crystal surface after 30 min. PC wet etching at 80 °C.

Boosting 5-Hydroxymethylfurfural Electrooxidation by Porous Biochar via Loading Numerous Surface-Exposed Cobalt Phosphonates.

The electrooxidation of 5-hydroxymethylfurfural (HMF) into 2,5-furandicarboxylic acid (FDCA) demonstrated its unique superiority, not only in reducing overpotential and improving energy conversion efficiency for green hydrogen production but also in utilizing abundant biomass resources and producing high-value-added chemicals. However, designing highly efficient electrocatalysts for HMF electrooxidation (HMF-EOR) with low cost and high performance for large-scale production remained a huge challenge. Herein, we introduced an easy one-step activation process to produce P-doped porous biochar loaded with multiple crystal surfaces exposed to CoP2O6 catalysts (CoP2O6@PC), which exhibited outstanding electrooxidation performance. To achieve a current density of 50 mA cm-2, only a low overpotential of 200 mV was needed for the electrooxidation of HMF in 1.0 M KOH + 10 mM HMF. This performance far surpassed that of other similar materials. CoP2O6@PC exhibited outstanding HMF-EOR performance with high conversion (nearly 100%), selectivity (97.1%), faradaic efficiency (95.3%), and robust stability. This work represents a promising strategy to fabricate macroscale and low-cost HMF-EOR electrocatalysts and achieve potential industrial applications of HMF-EOR.

The Effect of 147 MeV 84Kr and 24.5 MeV 14N Ions Irradiation on the Optical Absorption, Luminescence, Raman Spectra and Surface of BaFBr Crystals

Today, BaFBr crystals activated by europium ions are used as detectors that store absorbed energy in metastable centers. In these materials, the image created by X-ray irradiation remains stable in the dark for long periods at room temperature. As a result, memory image plates are created, and they are extended to other types of ionizing radiation as well. Despite significant progress towards X-ray storage and readout of information, the mechanisms of these processes have not been fully identified to date, which has hindered the efficiency of this class of phosphors. In this study, using photoluminescence (PL), optical absorption (OA), Raman spectroscopy (RS), and atomic force microscopy (AFM), the luminescence of oxygen vacancy defects to BaFBr crystals irradiated with 147 MeV 84Kr and 24.5 MeV 14N ions at 300 K to fluences (1010–1014) ion/cm2 was investigated. BaFBr crystals were grown by the Shteber method on a special device. Energy-dispersive X-ray spectroscopy (EDX) analysis revealed the presence of Ba, Br, F, and O. The effect of oxygen impurities present in the studied crystals was considered. The analysis of the complex PL band, depending on the fluence and type of ions, showed the formation of three types of oxygen vacancy defects. Macrodefects (tracks) and aggregates significantly influence the luminescence of oxygen vacancy defects. The creation of hillocks and tracks in BaFBr crystals irradiated with 147 MeV 84Kr ions is shown for the first time. Raman spectra analysis confirmed that BaFBr crystals were amorphized by 147 MeV 84Kr ions due to track overlap, in contrast to samples irradiated with 24.5 MeV 14N ions. Raman and absorption spectra demonstrated the formation of hole and electron aggregate centers upon swift heavy ions irradiation.

Synthesis and characterization of nitrogen-doped-MWCNT@cobalt oxide for nerve agent simulant detection

Organophosphorus nerve agents are toxic compounds that disrupt neuromuscular transmission by inhibiting the neurotransmitter enzyme, acetylcholinesterase, leading to rapid death. A hybrid composite was synthesized using a hydrothermal process for the early detection of dimethyl methyl phosphonate (DMMP), a simulant of the G-series nerve agent, sarin. Quartz crystal microbalance (QCM) and surface acoustic wave (SAW) sensors were used as detectors. Nitrogen-doped multiwalled carbon nanotubes (N-MWCNTs), cobalt oxide (Co3O4), and N-MWCNT@Co3O4 were compared to detect DMMP concentrations of 25–150 ppm. At 25 ppm, the differential frequencies (Δf) of the N-MWCNT, Co3O4, and N-MWCNT@Co3O4 sensors were 5.8, 2.3, and 99.5 Hz, respectively. The selectivity results revealed a preference for the DMMP rather than potential interference. The coefficients of determination (R2) of the N-MWCNT, Co3O4, and N-MWCNT@Co3O4 sensors for detecting 25–150 ppm DMMP were 0.983, 0.986, and 0.999, respectively. The response times of the N-MWCNT, Co3O4, and N-MWCNT@Co3O4 sensors for detecting 100 ppm DMMP were 25, 27, and 34 s, respectively, while the corresponding recovery times were 85, 105, and 181 s. The repeatability results revealed the reversible adsorption and desorption phenomena for the fixed DMMP concentration of 100 ppm. These unique findings show that synthesized materials can be used to detect organophosphorus nerve agents.

Studies of the Crystallization and Dissolution of Individual Suspended Sodium Chloride Aerosol Particles.

Aerosols transform between physical phases, as they respond to variations in environmental conditions. There are many industries that depend on these dynamic processes of crystallization and dissolution. Here, a single particle technique (an electrodynamic balance) is used to explore the crystallization and dissolution dynamics of a model system, sodium chloride. The physical and environmental factors that influence the dynamics of crystal formation from a saline droplet (whose initial radius is ∼25 μm) and the kinetics of water adsorption onto dried particles are examined. The drying relative humidity (RH) is shown to impact the physical properties of the dried particle. When a saline droplet is injected into an airflow at an RH close to the efflorescence RH (ERH, 45%), an individual single crystal forms. By contrast, when a compositionally equivalent saline droplet is injected into dry air (RH ∼ 0%), a salt crystal made of multiple crystalline particles is formed. Subsequent to crystallization, the crystal shape, morphology, and surface area were all found to affect the dissolution dynamics of the dried particle. Additionally, we report that the difference between the deliquesce RH and environmental RH significantly impacts the dissolution time scale.

Br-Vacancies Induced Variable Ranging Hopping Conduction in High-Order Topological Insulator Bi4Br4.

The defects have a remarkable influence on the electronic structures and the electric transport behaviors of the matter, providing the additional means to engineering their physical properties. In this work, a comprehensive study on the effect of Br-vacancies on the electronic structures and transport behaviors in the high-order topological insulator Bi4Br4 is performed by the combined techniques of the scanning tunneling microscopy (STM), angle-resolved photoemission spectroscopy (ARPES), and physical properties measurement system along with the first-principle calculations. The STM results show the defects on the cleaved surface of a single crystal and reveal that the defects are correlated to the Br-vacancies with the support of the simulated STM images. The role of the Br-vacancies in the modulation of the band structures has been identified by ARPES spectra and the calculated energy-momentum dispersion. The relationship between the Br-vacancies and the semiconducting-like transport behaviors at low temperature has been established, implying a Mott variable ranging hopping conduction in Bi4Br4. The work not only resolves the unclear transport behaviors in this matter, but also paves a way to modulate the electric conduction path by the defects engineering.

Tellurization of Pd(111) revisited: Formation of a TePd[formula omitted] surface alloy but no PdTe[formula omitted] monolayer

In a recent publication [2D Materials, 8, 045033 (2021)], it was reported that the growth of a monolayer PdTe2 in ultra-high vacuum could be achieved by deposition of tellurium on a palladium (111) crystal surface and subsequent thermal annealing. By means of low-energy electron diffraction intensity (LEED-IV) structural analysis, we show that the obtained 3×3R30° superstructure is in fact a TePd2 surface alloy. Attempts to produce a PdTe2 layer in ultra-high vacuum by increasing the Te content on the surface were not successful.

Laterally coupled photonic crystal surface emitting laser arrays

We propose and investigate a novel coherent laser array design based on laterally coupled photonic crystal surface-emitting lasers (PCSELs). As a new type of semiconductor laser technology, PCSELs have field confinement in a planar cavity and laser beam emission in the surface normal direction. By engineering lateral couplings between PCSELs with heterostructure photonic crystal designs, we can achieve coherent operations from an array of PCSELs. In this paper, we demonstrate coherent operation from a passively coupled PCSEL array design. We fabricated PCSEL array devices on a GaAs-based quantum well heterostructure at a target wavelength of 1040 nm. Experimental results show that the 2-by-2 PCSEL arrays have spectral linewidth of 0.14–0.22 nm. Beam combining performance was characterized by self-interference experiments. Similar coherency between the PCSEL array and single PCSEL device was observed. Our compact PCSEL array designs by passive lateral coupling have potential applications in fields of on-chip photonic computing, quantum, and information processing.

Effect of Fluorine and Phosphorus Impurities in Phosphogypsum on Microstructure and Mechanism of α‐Type Hemihydrate Gypsum Crystals

AbstractIn this study, phosphogypsum (PG) is simulated by doping fluorine and phosphorus ions in an analytically pure reagent of gypsum dihydrate. The influence of fluorine and phosphorus impurity and content on the dehydration reaction process of phosphogypsum and its crystalline micromorphology is assessed during the preparation of α‐type gypsum hemihydrate in the reversed‐phase microemulsion system and its mechanism. The results show that when the fluorine content increases from 0 to 1.0 mol L−1 (ωNaF = 1.0 mol L−1), the dehydration process of dihydrate gypsum will be greatly slowed down. Scanning electron microscopy (SEM) analysis showed that even a small amount of F− (ωNaF = 0.2 mol L−1) can significantly inhibit the formation of α‐type hemi‐hydrated gypsum. When ωH3PO4 = 0.10 mol L−1, the water of crystallization content in the solid phase of the sample decreased to 5.24% after 90 min, which is significantly lower than during the same period of the benchmark group. However, there is a threshold value for the effect of phosphorus on the microscopic morphology of the α‐type gypsum hemihydrate crystals, when ωH3PO4 ≤ 0.04 mol L−1, the crystal morphology is basically unaffected. Moreover, when ωH3PO4 continued to increase, the defects on the crystal surface increased.

Evidence for Magnetic Crystallization Waves at the Surface of $$^3$$He Crystal

AbstractUltralow temperature crystals of the helium isotopes $$^3$$ 3 He and $$^4$$ 4 He are intriguing quantum systems. Deciphering the complex features of these unusual materials has been made possible in large part by Alexander Andreev’s groundbreaking research. In 1978, Andreev and Alexander Parshin predicted the existence of melting/freezing waves at the surface of a solid $$^4$$ 4 He crystal, which was subsequently promptly detected. Successively, for the fermionic $$^3$$ 3 He superfluid/solid interface, even more intricate crystallization waves were anticipated, although they have not been observed experimentally so far. In this work, we provide preliminary results on $$^3$$ 3 He crystals at the temperature $$T = 0.41$$ T = 0.41 mK, supporting the existence of spin supercurrents in the melting/freezing waves on the crystal surface below the antiferromagnetic ordering temperature $$T_N= 0.93$$ T N = 0.93 mK, as predicted by Andreev. The spin currents that accompany such a melting-freezing wave make it a unique object, in which the inertial mass is distinctly different from the gravitational mass.

Features of the crystal structure and surface of superprotonic conductor caesium hydrogen sulfate phosphate.

The crystal structure of superprotonic conductor caesium hydrogen sulfate phosphate [Cs4(HSO4)3(H2PO4)] have been analyzed using neutron diffraction methods. Additionally, its structure and surface layers have been investigated using atomic force microscopy. From the diffraction data obtained, Fourier syntheses of neutron scattering densities were calculated, and the localization of hydrogen atoms and the parameters of three types of hydrogen bonds in the crystal structure were accurately determined. Correlation of surface characteristics of samples obtained by atomic force microscopy with their crystal structure is shown.

MOFs-Based Materials with Confined Space: Opportunities and Challenges for Energy and Catalytic Conversion.

Metal-Organic Frameworks (MOFs) are a very promising material in the fields of energy and catalysis due to their rich active sites, tunable pore size, structural adaptability, and high specific surface area. The concepts of "carbon peak" and "carbon neutrality" have opened up huge development opportunities in the fields of energy storage, energy conversion, and catalysis, and have made significant progress and breakthroughs. In recent years, people have shown great interest in the development of MOFs materials and their applications in the above research fields. This review introduces the design strategies and latest progress of MOFs are included based on their structures such as core-shell, yolk-shell, multi-shelled, sandwich structures, unique crystal surface exposures, and MOF-derived nanomaterials in detail. This work comprehensively and systematically reviews the applications of MOF-based materials in energy and catalysis and reviews the research progress of MOF materials for atmospheric water harvesting, seawater uranium extraction, and triboelectric nanogenerators. Finally, this review looks forward to the challenges and opportunities of controlling the synthesis of MOFs through low-cost, improved conductivity, high-temperature heat resistance, and integration with machine learning. This review provides useful references for promoting the application of MOFs-based materials in the aforementioned fields.

Regulation of fat crystals in water-in-oil emulsions by high-intensity ultrasound: Crystal size and tracing of droplet distribution

In this paper, two emulsion systems with high and low solid fat contents were prepared from 20 % water phase and 80 % oil phase by adjusting the palm oil/palm stearin/soybean oil ratio. Different ultrasonic power and time were used for the pretreatment of emulsion with different solid fat content, and the application characteristics of ultrasonic in W/O emulsions were explored and evaluated. Directly using high-intensity ultrasound to prepare fatty emulsions would weaken the hardness and storage modulus G' of the samples. Although ultrasound reduced the size of fat crystals in emulsions, the interaction between water droplets and fat crystals needs to be considered. After ultrasonic treatment, water droplets were difficult to immobilize on the crystal surface and thus acted as an active filler to stabilize the emulsion together with the fat crystal network. In high solid fat emulsion systems, an increase in ultrasound power (from 100 W to 200 W) could more affect the crystallization behavior of fats than an increase in ultrasound duration (from 30 s to 60 s), and the distribution of crystals and droplets was more uniform. In the low solid fat emulsion system, the texture of the sample after ultrasonic treatment was softer, and the surface was more delicate and smoother. However, the higher ultrasonic intensity (200 W) was not conducive to the preparation of the spread. Although the ultrasound with excessive intensity promoted the formation of small crystals, it would also lead to the aggregation of small crystals. These small crystals cannot form a uniform crystal network, which increases the fluidity of emulsions.

Morphological and Structural Characterization of (Pt, Au, and Ag) Nanoparticle/Zn-MOF-74 Composites.

Metallic nanoparticles (NPs) were decorated onto Zn-MOF-74 crystals by photoreducing different metal precursors (Pt, Au, and Ag) using ultraviolet (UV) light in an aqueous solution with different metal concentrations without using additional stabilizers. X-ray diffraction revealed the three-dimensional structural integrity and crystallinity conservation of Zn-MOF-74 crystals during the UV decoration process. Raman spectroscopy showed a minor rearrangement in the structure of the Zn-MOF-74 crystal surface after NP decoration. X-ray photoelectron spectroscopy confirmed the metal oxidation states of Zn and NPs. High-resolution transmission electron microscopy images proved the surface decoration of Zn-MOF-74 crystals with spherical metallic NPs with diameters between 2.4 and 9.8 nm.

Antireflection microstructures on ZnSe for mid- and far-IR fabricated by femtosecond laser ablation assisted with wet chemical etching

Most infrared materials used in high-power systems, such as optical parametric generators, have high values of refractive indices, which result in high Fresnel losses. The performance of conventional antireflection coatings is limited when used in high-power and ultra-broadband systems. An alternative approach is to fabricate antireflection microstructures (ARMs) that allow for a broadband increase in transmittance without reducing the damage threshold of the material. In this work, ARMs were fabricated on the surface of ZnSe crystals using the femtosecond laser ablation assisted with wet chemical etching method. This allowed to produce high aspect ratio microstructures that increase the transmittance up to 98% in the mid- and far- infrared regions.