Crystal Faces Research Articles

Vacuum diffusion bonding of TC4 titanium alloy to T2 copper with VCrNi1.8 eutectic medium entropy alloy interlayer

A new eutectic medium entropy alloy VCrNi1.8 was designed for vacuum diffusion bonding TC4 titanium alloy (TC4) with T2 copper (T2). The influence of welding parameters on the microstructure and shear strength of joints was investigated. β-Ti/Ti3Ni/Ti3AlNi/Ti2Ni/TiNi/TiNi(V, Cr)2/BCC + FCC/Ni(V, Cr)2/Cu phases existed in sequence in the TC4/VCrNi1.8/T2 joint. The crystallographic orientations of Ti3AlNi, Ti2Ni, TiNi and TiNi(V, Cr)2 phases were (200), (020), (011) and (012), respectively. The zone axis of Ti3AlNi, Ti2Ni, TiNi and TiNi(V, Cr)2 phases was correspondingly [002¯], [202], [100] and [4¯00]. The maximum shear strength of joint made at 880 °C for 90 min reached 214 MPa. The growth activation energy of diffusion zones I and II on TC4/VCrNi1.8 side was 230 kJ/mol and 246 kJ/mol, respectively. The interplanar spacing of (200), (020), (011) and (012) was d(200) = 0.656 nm, d(020) = 0.375 nm, d(011) = 0.556 nm and d(012) = 0.225 nm, respectively. The crystal face mismatch of Ti3AlNi/Ti2Ni, Ti2Ni/TiNi and TiNi/TiNi(V, Cr)2 interface was calculated to be 54.5%, 58.3% and 84.8%, respectively, revealing non-coherent with high strain energy. When the bonding temperature increased and holding time prolonged, the joint fractured along the TC4/VCrNi1.8 interface. The fracture morphology of joint presented cleavage fracture characteristics. The average diffusion coefficient of Cu in VCrNi1.8 interlayer at 840 °C, 860 °C, 880 °C, and 900 °C was 0.9 × 10−15 m2/s, 1.2 × 10−15 m2/s,1.6 × 10−15 m2/s, and 2.5 × 10−15 m2/s, respectively.

Rational Design of Transition-Metal-Based Catalysts for the Electrochemical 5-Hydroxymethylfurfural Reduction Reaction.

The electrochemical reduction reaction (HMFRR) of 5-hydroxymethylfurfural (HMF) has emerged as a promising avenue for the utilization and refinement of the biomass-derived platform molecule HMF into high-value chemicals, addressing energy sustainability challenges. Transition metal electrocatalysts (TMCs) have recently garnered attention as promising candidates for catalyzing HMFRR, capitalizing on the presence of vacant d orbitals and unpaired d electrons. TMCs play a pivotal role in facilitating the generation of intermediates through interactions with HMF, thereby lowering the activation energy of intricate reactions and significantly augmenting the catalytic reaction rate. In the absence of comprehensive and guiding reviews in this domain, this paper aims to comprehensively summarize the key advancements in the design of transition metal catalysts for HMFRR. It elucidates the mechanisms and pH dependency of various products generated during the electrochemical reduction of HMF, with a specific emphasis on the bond-cleavage angle. Additionally, it offers a detailed introduction to typical in-situ characterization techniques. Finally, the review explores engineering strategies and principles to enhance HMFRR activity using TMCs, particularly focusing on multiphase interface control, crystal face control, and defect engineering control. This review introduces novel concepts to guide the design of HMFRR electrocatalysts, especially TMCs, thus promoting advancements in biomass conversion.

A novel morphology of high voltage LiMn1.5Ni0.5O4 cathode material with niobium-doping

Spinel LiMn1.5Ni0.5O4 (LMNO) is one of the promising cathode materials for the next generation Li-ion batteries due to its voltage platform. However, the dissolution of the transition metal at high voltage is the biggest obstacle that LMNO suffers from. In this study, we successfully suppressed transition metal dissolution in LMNO by the morphology control from regular octahedron to spherical. Niobium was integrated as a dopant, which restricted the growth of (111) crystal face, and increased the indices of crystal faces by homogenizing the surface energy. By changing to a smaller surface area with spherical morphology, the contact area with the electrolyte was reduced, thus suppressing the dissolution of the Mn ion. Consequently, the niobium-doped LMNOexhibited superior rate performance, capacity retention with 74.1% at 1C after 500 cycles in half-cell, and thermal stability compared to pristine LMNO.

Boosting CO2 methanation activity by tuning Ni crystal plane and oxygen vacancy in Ni/CeO2 catalyst

It is challenging to boost CO2 methanation activity over Ni-based catalysts, and new findings that decipher the relationship between the essential laws of catalysts and their catalytic performance will be transformative. Herein, three kinds of Ni/CeO2 catalysts with different Ni crystal facets and oxygen vacancy are developed by varied preparation methods, which show significant differences in catalytic performance for CO2 methanation, and these catalysts are taken as a case study for the investigation of the crystal plane and oxygen vacancy effects in CO2 methanation as well. It is observed that the activity of Ni/CeO2-SG catalyst with abundant oxygen vacancies and principally exposed Ni (111) crystal facet is highly active for CO2 methanation reaction, which is 1–3 times than that of Ni/CeO2 catalysts with poor oxygen vacancy and/or Ni (111) crystal face. In addition, the former one cannot suffer from deactivation even in operation 130 h at 300 °C. Both structural investigations and catalytic evaluations indicate that the adsorption and activating ability of H2 and CO2 can be controlled by adjusting the Ni-exposed crystal face and oxygen vacancy concentration, respectively. It is also verified that the synergistic contribution of the Ni crystal facets and the oxygen vacancy play a crucial role in boosting the catalytic activity of the Ni/CeO2 catalysts by affecting the adsorption and activation of reactants. The Ni/CeO2 catalysts exposed Ni (111) crystal plane facilitate the catalytic activity by strengthing the H2 adsorption/dissociation capacity, while the abundantly available oxygen vacancies maximize the activity via acting as CO2 activation sites. Furthermore, the in situ DRIFT experiments reveal that the direct formate hydrogenation pathway is involved in the CO2 methanation process over the Ni/CeO2-SG catalyst.

Machine learning accelerates the screening of efficient metal-oxide catalysts for photocatalytic water splitting

Photocatalytic water splitting represents a sustainable avenue for hydrogen production, yet the traditional trial-and-error approach for identifying efficient photocatalysts among numerous candidates is cumbersome. In this paper, we introduce a machine learning (ML)-driven approach for rapid screening of promising metal oxide photocatalysts for hydrogen generation. This methodology comprises three key steps: the construction of a comprehensive material library, ML-accelerated material screening, and Density Functional Theory (DFT) calculations for verification. Through this process, we successfully identify ten metal oxides with good energy levels and charge carrier transport properties from an initial library of 860 candidates. Notably, CsYO2 emerges as a standout candidate, exhibiting excellent photocatalytic water-splitting performance on its (001) crystal face, with Y atoms identified as active sites through DFT calculations. This study demonstrates the efficacy of applying machine learning to the precise and rapid screening of vast material databases, paving the way for discovering novel and efficient photocatalysts.

Deactivation of layered MnO2 catalyst during room temperature formaldehyde degradation and its thermal regeneration mechanism

Layered δ-MnO2 prepared by a one-step redox method was shown to be deactivated during oxidation of formaldehyde at room temperature. Recovery of the formaldehyde degradation activity was investigated after thermal regeneration at different temperatures. XRD, SEM, TEM, H2-TPR, XPS, TGA and DRIFTS characterization were used to analyze the physical properties of fresh, deactivated and thermally regenerated catalysts. The results showed that deactivation of catalyst was caused by less oxygen vacancies due to increased Mn4+ content during formaldehyde degradation and formation of formate blocking active sites. Thermal regeneration helped to decompose formate at the catalyst surface, restoring some of the active sites. Interplanar spacing of MnO2 became wider and the number of Mn3+ on exposed crystal faces increased. More oxygen vacancies were formed. The activity of deactivated catalyst was restored. Formaldehyde degradation rate of catalyst regenerated at 200 °C remained above 80 % after 6 h, demonstrating the possibility of waste layered catalyst recycling.

Exploring surface properties and premelting in crystals.

Crystal surfaces play a pivotal role in governing various significant processes, such as adsorption, nucleation, wetting, friction, and wear. A fundamental property that influences these processes is the surface free energy, γ. We have directly calculated γ(T) for low-index faces of Lennard-Jones (LJ), germanium, and silicon crystals along their sublimation lines using the computational cleavage technique. Our calculations agree well with experimental values for Si(111) and Ge(111), highlighting the accuracy of the method and models used. For LJ crystals, we identified a premelting onset at Tpm = 0.75Tm, marked by a sharp increase in atom mobility within the second outermost surface layer. Notably, Tpm closely aligned with the endpoint of the LJ melting line at negative pressures, Tend = 0.76Tm. We hypothesize that the emergence and coexistence of a liquid film atop the LJ crystal at Tpm < T < Tm correspond to the metastable melting line under negative pressures experienced by stretched crystal surfaces. Furthermore, our study of thin LJ crystal slabs reveals that premelting-induced failure leads to recrystallization below the homogeneous freezing limit, offering a promising avenue to explore crystal nucleation and growth at extremely deep supercoolings. Finally, no evidence of premelting was detected in the model crystals of Ge and Si, which is consistent with the experimental observations. Overall, our findings offer valuable insights into crystal surface phenomena at the atomic scale.

Heterogeneous nucleation interface between NbN(111) and TiN(111) in high-nitrogen austenitic stainless steels: First-principles calculation

Heterogeneous nucleation of NbN induced by TiN inclusions is important to play the role of precipitation strengthening in high-nitrogen austenitic stainless steels. In this work, the atomic structure, interfacial stability, and interfacial fracture toughness of TiN(111)/NbN(111) are investigated based on first-principles calculation. Furthermore, the interfacial bond structure and energy of TiN(111)/NbN(111) are also analyzed with and without Cr doping on the basis of Thermo-Calc phase diagrams. The results indicate that the lattice mismatch between the crystal face of TiN(111) and NbN(111) is lower than 5 %, which reveals that TiN can act as the heterogeneous nucleus for NbN to grow. Besides, the maximum adhesion work at 4.58 J/m2 and the minimum interfacial energy at 1.28 J/m2 are presented on the stacking site of N-Ti TL, which suggests that (Ti, Nb) N phases can precipitate through this interfacial bonding mode. Moreover, from the view of bonding properties on the interface with and without Cr doping, it can be found Cr doping in two layers of the interface can enhance interface stability except for N-Ti TL (2Cr). This work will give promising guidance and theoretical basis for the controllable preparation of high-nitrogen austenitic stainless steels with in-situ precipitated nitride particles.

Selective exposure of (1 1 1) crystal plane in Pd49Ag30Te4 by Tb doping to weaken Pd − C bond and promote electroreduction of CO2 to CO

Employing electric energy to convert carbon dioxide (CO2) into valuable small molecules is a potentially practical method in energy storage and greenhouse gas alleviation. A huge challenge for electrocatalytic CO2 reduction is to reduce overpotential to improve energy efficiency. Herein, we demonstrate that doping alloy Pd49Ag30Te4 (PAT) with rare-earth element Tb is beneficial for selective exposure of (111) crystal plane, which is a highly active crystal plane for producing carbon monoxide (CO). The as-prepared Tb2.9PAT exhibited high electrocatalytic performance with 95.7 % CO faradic efficiency at − 0.8 V (vs RHE), far exceeding that of PAT, and coupled with good durability. In situ spectral study and theoretical calculations disclose that the introduction of Tb regulates the d-band center of PAT alloy, weakens the Pd − C bonding ability, and promotes the desorption of *CO in the rate-determining step. This study provides a method for doping induced selective exposure of crystal face, which provides new idea for improving catalytic performance.

Study on the mechanism of controlling the morphology of basic magnesium carbonate prepared under different hydration conditions

Basic magnesium carbonate is gaining prominence in flame retardant materials due to its excellent flame-retardant properties and clean decomposition products. This study investigates a hydration-carbonation method to address challenges related to the preparation, morphology control, and stability of magnesium basic carbonate. The impact of hydration conditions on the morphology of the carbonate was analyzed using scanning electron microscopy (SEM) and X-ray diffraction (XRD). The results indicate that spherical magnesium basic carbonate with regular morphology and uniform particle size can be achieved at a hydration temperature of 50°C for 1.5 hours. However, extending the hydration time and increasing the temperature resulted in irregular morphologies. Molecular dynamics simulations using the CASTEP and Forcite modules of Materials Studio were employed to understand the influence of hydration-carbonation conditions on the carbonate's morphology. The simulations revealed that the (1 1 1) and (2 0 0) crystal faces of MgO, with higher surface energies, promote the formation of precursor magnesium hydroxide nuclei, leading to heterogeneous magnesium alkali carbonate at elevated temperatures. Prolonged hydration time resulted in fragmented carbonate structures. To control the morphology of magnesium alkali carbonate, it is essential to optimize hydration temperature and duration. The simulation results corroborate experimental findings, providing deeper insights into the liquid-gas-solid adsorption relationships during the carbonation process. This study offers valuable guidelines for the controlled synthesis of magnesium basic carbonate, enhancing its applicability in flame retardant materials.

Growth of Size-Tunable Ag2O Polyhedra and Revelation of Their Bulk and Surface Lattices.

By primarily adjusting the reagent amounts, particularly the volume of AgNO3 solution introduced, Ag2O cubes with decreasing sizes from 440 to 79 nm, octahedra from 714 to 106 nm, and rhombic dodecahedra from 644 to 168 nm are synthesized. 733 nm cuboctahedra are also prepared for structural analysis. With in-house X-ray diffraction (XRD) peak calibration, shape-related peak shifts are recognizable. Synchrotron XRD measurements at 100 K reveal the presence of bulk and surface layer lattices. Bulk cell constants also deviate slightly. They show a negative thermal expansion behavior with shrinking cell constants at higher temperatures. The Ag2O crystals exhibit size- and facet-dependent optical properties. Bandgaps red-shift continuously with increasing particle sizes. Optical facet effect is also observable. Moreover, synchrotron XRD peaks of a mixture of Cu2O rhombicuboctahedra and edge- and corner-truncated cubes exposing all three crystal faces can be deconvoluted into three components with the bulk and the [111] microstrain phase as the major component. Interestingly, while the unheated Cu2O sample shows clear diffraction peak asymmetry, annealing the sample to 450 K yields nearly symmetric peaks even when returning the sample to room temperature, meaning even moderately high temperatures can permanently change the crystal lattice.

In-layer inhomogeneity of molecular dynamics in quasi-liquid layers of ice

Quasi-liquid layers (QLLs) are present on the surface of ice and play a significant role in its distinctive chemical and physical properties. These layers exhibit considerable heterogeneity across different scales ranging from nanometers to millimeters. Although the formation of partially ice-like structures has been proposed, the molecular-level understanding of this heterogeneity remains unclear. Here, we examined the heterogeneity of molecular dynamics on QLLs based on molecular dynamics simulations and machine learning analysis of the simulation data. We demonstrated that the molecular dynamics of QLLs do not comprise a mixture of solid- and liquid water molecules. Rather, molecules having similar behaviors form dynamical domains that are associated with the dynamical heterogeneity of supercooled water. Nonetheless, molecules in the domains frequently switch their dynamical state. Furthermore, while there is no observable characteristic domain size, the long-range ordering strongly depends on the temperature and crystal face. Instead of a mixture of static solid- and liquid-like regions, our results indicate the presence of heterogeneous molecular dynamics in QLLs, which offers molecular-level insights into the surface properties of ice.

High-Performance Hard X-Ray Imaging Detector Using Facet-Dependent Bismuth Vanadate.

Bismuth vanadate (BiVO4) exhibits large absorption efficiency for hard X-rays, which endows it with a robust capacity to attenuate X-ray radiation across a broad energy range. The anisotropic properties of BiVO4 allow for the manipulation of their physical and chemical characteristics through crystallographic orientation and exposed facets. In this study, the issue of heavy recombination caused by sluggish electron transport in BiVO4 is successfully addressed by enhancing the abundance of the (040) crystal face ratio using a Co2+ crystal face exposure agent. The facet-dependent modifications exhibit excellent and balanced intrinsic charge transport properties, and finely optimize both the sensitivity and detection limit of BiVO4 X-ray detectors. As a result, ultra-stable BiVO4 metal oxide X-ray detectors demonstrate a high sensitivity of 3164 µC Gyair -1 cm-2 and a low detection limit of 20.76 nGyair s-1 under 110 kVp hard X-rays, establishing a new benchmark for X-ray detectors based on polycrystalline Bi-halides and metal oxides. These findings highlight the significance of crystal orientation in optimizing materials for X-ray detection, setting a new sensitivity record for X-ray detectors based on polycrystalline Bi-halides and metal oxides, which paves the way for the development of advanced, low-dose, and highly stable imaging systems specifically for hard X-rays.

Surface characteristics and material removal mechanisms during nanogrinding on C-face and Si-face of 4H-SiC crystals: Experimental and molecular dynamics insights

4H-SiC wafers hold significant promise for applications in power devices and radiofrequency devices. In order to develop a cost-effective and efficient grinding technology for 4H-SiC wafers, it is imperative to thoroughly investigate the mechanisms underlying damage evolution on different crystal faces of 4H-SiC. Our approach involved employing a range of experimental techniques including nanoindentation, scratching, and grinding, coupled with molecular dynamics (MD) simulation to systematically analyze the material removal mechanisms on both the C-face and Si-face. Through a comprehensive comparison of mechanical properties, surface morphology, and subsurface damage distribution between the C-face and Si-face, we uncovered the plastic deformation mechanisms operating on each face. Our research findings emphasize that, compared to the Si-face, the C-face exhibits higher elastic modulus and hardness, but lower fracture toughness. Additionally, due to the C-face’s greater propensity for high-density dislocation formation compared to the Si-plane, stress release occurs in the machining area, resulting in smaller normal forces and aiding in reducing surface roughness after grinding. This study provides important guidance for the grinding of the two critical basal planes of single-crystal 4H-SiC.

Dendrite-free Zn anode enabled by combining carbon nanoparticles hydrophobic layer with crystal face reconstruction toward high-performance Zn-ion battery

Aqueous zinc ion batteries (ZIBs) have been considered promising energy storage systems due to their excellent electrochemical performance, environmental toxicity, high safety and low cost. However, uncontrolled dendrite growth and side reactions at the zinc anode have seriously hindered the development of ZIBs. Herein, we prepared the carbon nanoparticles layer coated zinc anode with (103) crystal plane preferential oriented crystal structure (denoted as C@RZn) by a facile one-step vapor deposition method. The preferential crystallographic orientation of (103) crystal plane promotes zinc deposition at a slight angle, effectively preventing the formation of Zn dendrites on the surface. In addition, the hydrophobic layer of carbon layer used as an inert physical barrier to prevent corrosion reaction and a buffer during volume changes, thus improving the reversibility of the zinc anode. As a result. the C@RZn anode achieves a stable cycle performance of more than 3000 h at 1 mA cm−2 with CE of 99.77 % at 5 mA cm−2. The full battery with C@RZn anode and Mn-doped V6O13 (MVO) cathode show stability for 5000 cycles at the current density of 5 A g−1. This work provides a new approach for the design of multifunctional interfaces for Zn anode.

Online Orientation Recognition of Single-Crystal Diamond Tools in the Process of Indexing Grinding Based on HMM and Multi-Information Fusion

Single-crystal diamond tools occupy an important position in the field of optical processing as the basis and key to advanced optical manufacturing technology, such as grating manufacturing and optical mirror-turning processing. Single-crystal diamond tools have become the cornerstone of the development of related industries. This paper takes a single-crystal diamond arc tool as the research object. Sound signal analysis technology and vibration signal analysis technology are comprehensively applied to the online orientation identification of a single-crystal diamond tool in the indexing grinding process. The online orientation method of the tool is explored, the sound signal and the vibration signal are taken as the characteristic signals, and a wavelet algorithm (WT) is used to reduce the noise of the vibration signal and sound signal. The kurtosis of the sound signal and the kurtosis and skewness of the vibration signal in the high-order statistics strongly related to the grinding direction of a single-crystal diamond are used as the characteristic parameters, and the online direction recognition model of the tool is established using the Hidden Markov Method (HMM). The above characteristic parameters are used as model input for multi-information fusion. The mapping relationship between the characteristic parameters of the characteristic signal and the crystal orientation of the single-crystal diamond crystal face is obtained, and then the online orientation method of the single-crystal diamond arc tool in the process of indexing grinding is formed. The effectiveness of the method is verified by experiments, and effective orientation information is provided for research on the positioning control strategy of the tool grinding process to ensure the efficiency of grinding and improve the manufacturing level of the tool.

Origin and Nucleation Kinetics of Transcrystalline Layer in Bamboo fiber@nano‐TiO2/Polypropylene Composite

AbstractHerein origin and nucleation kinetics of transcrystalline layer (TCL) in bamboo fiber deposited with nano‐TiO2 (BF@TiO2)/polypropylene (PP) composite is studied. Firstly, the surface morphology, roughness, and energy, as well as crystalline structure (e. g., crystal face indices (hkl)) of BF@TiO2 are analyzed to clarify the origin of TCL in the composite. Subsequently, the nucleation kinetics of TCL in BF@TiO2/PP composite at different crystallization temperatures (Tc) are investigated through polarized optical microscopy. The results find that the surface roughness and energy of BF@TiO2 increase by 47.55 % and 2.41 % compared with untreated BF, respectively. Interestingly, the mismatch rates (MRs) of hkl(BF) vs. hkl(PP) are &gt;320 %. In comparison, the MRs of (101)(BF@TiO2)TiO2 vs. (hkl)(PP) are dramatically decreased to &lt;25 %, suggesting a similar crystal plane between BF@TiO2 and PP matrix. These results indicate that the TCL formation in the composite is more facile in BF@TiO2 than in the untreated BF. During isothermal crystallization, the nucleation and spherulite growth rates decrease as the Tc increases. The interface free energy difference (▵σ) between BF@TiO2 and PP is calculated based on the heterogeneous nucleation theory. The ▵σ is 1.54±0.11 J cm−2, highlighting that the BF@TiO2 strongly induces the PP nucleation.

Tandem Electric-Fields Prolong Energetic Hot Electrons Lifetime for Ultra-Fast and Stable NO2 Detection.

Prolonging energetic hot electrons lifetimes and surface activity in the reactive site can overcome the slow kinetics and unfavorable thermodynamics of photo-activated gas sensors. However, bulk and surface recombination limit the simultaneous optimization of both kinetics and thermodynamics. Here tandem electric fields are deployed at (111)/(100)Au-CeO2 to ensure a sufficient driving force for carrier transfer and elucidate the mechanism of the relationship between charge transport and gas-sensing performance. The asymmetric structure of the (111)/(100)CeO2 facet junction provides interior electric fields, which facilitates electron transfer from the (100)face to the (111)face. This separation of reduction and oxidation reaction sites across different crystal faces helps inhibit surface recombination. The increased electron concentration at the (111)face intensifies the interface electric field, which promotes electron transfer to the Au site. The local electric field generated by the surface plasmon resonance effect promotes the generation of high-energy energy hot-electrons, which maintains charge concentration in the interface field by injecting into (111)/(100)CeO2, thereby provide thermodynamic contributions and inhibit bulk recombination. The tandem electric fields enable the (111)/(100)Au-CeO2 to rapidly detect 5ppm of NO2 at room temperature with stability maintained within 20s.

Pt/Al2O3 as efficient catalyst for the dehydrogenation of Dodecahydro-N-ethylcarbazole

The use of dodecahydro-N-ethylcarbazole in hydrogen storage for liquid organic hydrogen carrier systems holds potential for achieving large-scale application. In order to investigate the relationship between dodecahydro-N-ethylcarbazole dehydrogenation performance and Pt particles size, a series of monometallic Pt/Al2O3 catalysts with different Pt particles size from 0.70 nm to 5.12 nm were controlled synthesized by a simple impregnation method. The obtained catalysts are systematically characterized via XRD, 27Al MAS NMR, SEM-EDS, TEM, N2-adsorption, CO-IR, H2-TPR and NH3-TPD analyses, which provide essential micro-structure of these catalysts. The dehydrogenation of dodecahydro-N-ethylcarbazole over Pt/Al2O3 is a typical consecutive reaction, which follows a reaction sequence of dodecahydro-N-ethylcarbazole → octahydro-N-ethylcarbazole → tetrahydro-N-ethylcarbazole → N-ethylcarbazole. These dehydrogenation steps are quite sensitive to the Pt particle size. Large Pt particle can greatly enhance the reaction rates in octahydro-N-ethylcarbazole → tetrahydro-N-ethylcarbazole and tetrahydro-N-ethylcarbazole → N-ethylcarbazole steps. However, these two steps are difficult to take place in small Pt particles. The high performance of large Pt particle in dehydrogenation can be ascribed to its highly exposed (111) crystal face. The optimized catalyst Pt5.0/γ-Al2O3 with Pt average size of 4.63 nm demonstrated exceptional performance in dodecahydro-N-ethylcarbazole dehydrogenation at 180 °C and 101 kPa, and the dodecahydro-N-ethylcarbazole conversion of 100 %, N-ethylcarbazole selectivity of 96.44 % and dehydrogenation efficiency of 98.73 % can be achieved. These results provide valuable insights for the development of efficient metal-based catalysts for liquid organic hydrogen carriers hydrogen storage system.

Capture of single Ag atoms through high-temperature-induced crystal plane reconstruction

The “terminal hydroxyl group anchoring mechanism” has been studied on metal oxides (Al2O3, CeO2) as well as a variety of noble and transition metals (Ag, Pt, Pd, Cu, Ni, Fe, Mn, and Co) in a number of generalized studies, but there is still a gap in how to regulate the content of terminal hydroxyl groups to influence the dispersion of the active species and thus to achieve optimal catalytic performance. Herein, we utilized AlOOH as a precursor for γ-Al2O3 and induced the transformation of the exposed crystal face of γ-Al2O3 from (110) to (100) by controlling the calcination temperature to generate more terminal hydroxyl groups to anchor Ag species. Experimental results combined with AIMD and DFT show that temperature can drive the atomic rearrangement on the (110) crystal face, thereby forming a structure similar to the atomic arrangement of the (100) crystal face. This resulted in the formation of more terminal hydroxyl groups during the high-temperature calcination of the support (Al-900), which can capture Ag species to form single-atom dispersions, and ultimately develop a stable and efficient single-atom Ag-based catalyst.