Low-Temperature Acetylene Semi-Hydrogenation over the Pd1-Cu1 Dual-Atom Catalyst.

The atomically dispersed metal catalyst or single-atom catalyst (SAC) with the utmost metal utilization efficiency shows excellent selectivity toward ethylene compared to the metal nanoparticles catalyst in the acetylene semi-hydrogenation reaction. However, these catalysts normally work at relatively high temperatures. Achieving low-temperature reactivity while preserving high selectivity remains a challenge. To improve the intrinsic reactivity of SACs, rationally tailoring the coordination environments of the first metal atom by coordinating it with a second neighboring metal atom affords an opportunity. Here, we report the fabrication of a dual-atom catalyst (DAC) that features a bonded Pd1-Cu1 atomic pair anchoring on nanodiamond graphene (ND@G). Compared to the single-atom Pd or Cu catalyst, it exhibits increased reactivity at a lower temperature, with 100% acetylene conversion and 92% ethylene selectivity at 110 °C. This work provides a strategy for designing DACs for low-temperature hydrogenation by manipulating the coordination environment of catalytic sites at the atomic level.

Residual Learning and Multi-Path Feature Fusion-Based Channel Estimation for Millimeter-Wave Massive MIMO System.

Channel estimation is a challenging task in a millimeter-wave (mm Wave) massive multiple-input multiple-output (MIMO) system. The existing deep learning scheme, which learns the mapping from the input to the target channel, has great difficulty in estimating the exact channel state information (CSI). In this paper, we consider the quantized received measurements as a low-resolution image, and we adopt the deep learning-based image super-resolution technique to reconstruct the mm Wave channel. Specifically, we exploit a state-of-the-art channel estimation framework based on residual learning and multi-path feature fusion (RL-MFF-Net). Firstly, residual learning makes the channel estimator focus on learning high-frequency residual information between the quantized received measurements and the mm Wave channel, while abundant low-frequency information is bypassed through skip connections. Moreover, to address the estimator's gradient dispersion problem, a dense connection is added to the residual blocks to ensure the maximum information flow between the layers. Furthermore, the underlying mm Wave channel local features extracted from different residual blocks are preserved by multi-path feature fusion. The simulation results demonstrate that the proposed scheme outperforms traditional methods as well as existing deep learning methods, especially in the low signal-to-noise-ration (SNR) region.

FCNet: Stereo 3D Object Detection with Feature Correlation Networks.

Deep-learning techniques have significantly improved object detection performance, especially with binocular images in 3D scenarios. To supervise the depth information in stereo 3D object detection, reconstructing the 3D dense depth of LiDAR point clouds causes higher computational costs and lower inference speed. After exploring the intrinsic relationship between the implicit depth information and semantic texture features of the binocular images, we propose an efficient and accurate 3D object detection algorithm, FCNet, in stereo images. First, we construct a multi-scale cost-volume containing implicit depth information using the normalized dot-product by generating multi-scale feature maps from the input stereo images. Secondly, the variant attention model enhances its global and local description, and the sparse region monitors the depth loss deep regression. Thirdly, for balancing the channel information preservation of the re-fused left-right feature maps and computational burden, a reweighting strategy is employed to enhance the feature correlation in merging the last-layer features of binocular images. Extensive experiment results on the challenging KITTI benchmark demonstrate that the proposed algorithm achieves better performance, including a lower computational cost and higher inference speed in 3D object detection.

The Facile Dissociation of Carbon-Oxygen Bonds in CO2 and CO on the Surface of LaCoSiHx Intermetallic Compound.

In catalysis science, the electronic structure of the active site determines the structure-activity relationship of the catalyst to a large extent. Therefore, modulating the electronic structure has become a main route for the rational design of metal-based catalyst materials. In this work, we prepared a LaCoSiHx material that has more electronegativity and a lower workfunction than traditional supported Co-based catalysts. Using CO2 methanation as a model catalytic reaction, the facile dissociation of CO2 and CO (a key reaction intermediate) on the surface of the LaCoSiHx catalyst is observed by various experimental methods (e.g., in situ Raman and FTIR) at room temperature. Moreover, theoretical calculation results further show that LaCoSiHx has a much stronger capacity for carbon-oxygen bond activation than the Co surface. The intrinsic mechanism is attributed to the marked electron transfer from catalysts into the antibonding orbital of CO2 and CO.

Atomically Dispersed Pd on Nanodiamond/Graphene Hybrid for Selective Hydrogenation of Acetylene.

We reported here a strategy to use a defective nanodiamond-graphene (ND@G) to prepare an atomically dispersed metal catalyst, i.e., in the current case atomically dispersed palladium catalyst which is used for selective hydrogenation of acetylene in the presence of abundant ethylene. The catalyst exhibits remarkable performance for the selective conversion of acetylene to ethylene: high conversion (100%), ethylene selectivity (90%), and good stability. The unique structure of the catalyst (i.e., atomically dispersion of Pd atoms on graphene through Pd-C bond anchoring) blocks the formation of unselective subsurface hydrogen species and ensures the facile desorption of ethylene against the overhydrogenation to undesired ethane, which is the key for the outstanding selectivity of the catalyst.

Thermally Reversible and Irreversible Phase Transition Behaviors in Poly(ethylene oxide)/Ionic Liquid Mixtures.

The irreversible and reversible phase transition behaviors during phase separation-recovery (heating-cooling) cycles for poly(ethylene oxide)/1-ethyl-3-methylimidazolium tetrafluoroborate ionic liquid (PEO/[EMIM][BF4 ]) mixtures with a lower critical solution temperature phase diagram are reported for the first time. The evident differential scanning calorimetry endothermic and exothermic peaks are observed during the heating-cooling scan cycles near the phase boundary, in which the large heat loss for samples below the critical composition (60 wt% PEO) and obvious downward shift of phase transition temperature for all the compositions between the first and second cycles are particularly attractive. After the first recovery process, a reversible behavior during the next cycles is expected. These interesting phenomena are further confirmed by optical microscopy and Fourier-transform infrared measurements. It is demonstrated that the disruption and partial recovery of the hydrogen bonds, combined with the conformational change of PEO chains, can contribute to this irreversible behavior as well as a conversion to reversible phase transition behavior.

Unusual phase separation and rheological behavior of poly(ethylene oxide)/ionic liquid mixtures with specific interactions.

The phase separation behavior of poly(ethylene oxide) (PEO) in ionic liquid 1-ethyl-3-methylimidazolium tetrafluoroborate ([EMIM][BF4]) was investigated by rheological, optical microscopy, FT-IR and DSC measurements. It is demonstrated that specific interactions, particularly the hydrogen bonding between PEO and the ionic liquids as evidenced by FT-IR, in which a subtle but apparent absorption peak shift near the phase transition appears, account for the unusual low critical solution temperature (LCST) phase separation. Unlike the typical trend in which the storage modulus G' simply increases with temperature near the phase boundary for polymer blends without specific interaction, in our study, a novel "V-shaped" rheological response is observed, namely a dip in G' followed by an upturn, especially at low PEO concentration (<50 wt%). The magnitude of the "V" dip has heating rate and frequency dependences, while Tr (the phase transition temperature) is almost unchanged with heating rate and frequency. Upon increasing the alkyl chain length on the imidazolium ring from an ethyl to a butyl, the "V-shape" becomes more prominent and shifts to higher temperature, which is consistent with the results of FT-IR and DSC, evidently due to the stronger hydrogen bonding interaction between PEO and [BMIM][BF4] than [EMIM][BF4]. This unusual "V" dip might be tentatively ascribed to the coupling effects of the breaking of the "hydrogen bonding cage" formed between PEO chains and IL molecules and dissolution of the heterogeneous clusters as verified by FT-IR and TEM, respectively, and the following upturn is dominated by the interface formation upon phase separation.

Analysis of the convergence rules of full-range PSD surface error of magnetorheological figuring KDP crystal.

A new non-aqueous and abrasive-free magnetorheological finishing (MRF) method is adopted for processing potassium dihydrogen phosphate (KDP) crystal due to its low hardness, high brittleness, temperature sensitivity, and water solubility. This paper researches the convergence rules of the surface error of an initial single-point diamond turning (SPDT)-finished KDP crystal after MRF polishing. Currently, the SPDT process contains spiral cutting and fly cutting. The main difference of these two processes lies in the morphology of intermediate-frequency turning marks on the surface, which affects the convergence rules. The turning marks after spiral cutting are a series of concentric circles, while the turning marks after fly cutting are a series of parallel big arcs. Polishing results indicate that MRF polishing can only improve the low-frequency errors (L>10 mm) of a spiral-cutting KDP crystal. MRF polishing can improve the full-range surface errors (L>0.01 mm) of a fly-cutting KDP crystal if the polishing process is not done more than two times for single surface. We can conclude a fly-cutting KDP crystal will meet better optical performance after MRF figuring than a spiral-cutting KDP crystal with similar initial surface performance.

A simplified and facile preparation method for the [Ca24Al28O64]4+(e-)4 electride.

Wide application of novel materials often requires low-cost preparation methods. In this study, we present a simplified and facile preparation method for the [Ca24Al28O64]4+(e-)4 electride material (C12A7:e-). Successful preparation of the C12A7:e- electride was confirmed by XRD patterns and magnetic behavior analysis. The concentration of electrons in the prepared C12A7:e- powder was calculated to be approximately 2.23 × 1021 cm-3, as evaluated by iodometry and TPD. DFT calculations provided insight into the unique electronic structure of C12A7:e-. Additionally, the substitution of the Ca reductant with CaH2 led to a reduction in the solid-state reaction temperature from 1100 to 950 °C, which can be attributed to thermodynamic effects such as a reduction in ΔG°.

First-Principles Study of Three-Dimensional Electrides Containing One-Dimensional [Ba3N]3+ Chains.

Electrides, a unique type of compound where electrons act as anions, have a high electron mobility and a low work function, which makes them promising for applications in electronic devices and high-performance catalysts. The discovery of novel electrides and the expansion of the electride family have great significance for their promising applications. Herein, we reported four three-dimensional (3D) electrides by coupling crystal structure database searches and first-principles electronic structure analysis. Subnitrides (Ba3N, LiBa3N, NaBa3N, and Na5Ba3N) containing one-dimensional (1D) [Ba3N]3+ chains are identified as 3D electrides for the first time. The anionic electrons are confined in the 3D interstitial space of Ba3N, LiBa3N, NaBa3N, and Na5Ba3N. Interestingly, with the increase of Na content, the excess electrons of Na5Ba3N play two roles of metallic bonding and anionic electrons. Therefore, the subnitrides containing 1D [Ba3N]3+ chains can be regarded as a new family of 3D electrides, where anionic electrons reside in the 3D interstitial spaces and provide a conduction path. These materials not only are experimentally synthesizable 3D electrides but also are promising to be exfoliated into advanced 1D nanowire materials. Furthermore, our work suggests a discovery strategy of novel electrides based on one parent framework like [Ba3N]3+ chains, which would accelerate the mining of electrides from the crystal structure database.

PLCζ can stably regulate Ca2+ fluctuations in early embryo.

Phospholipase C zeta (PLCζ) is an important inducer of Ca2+ oscillations in mammalian sperm. To explore the influence of PLCζ on early embryonic Ca2+ fluctuations during sperm-egg binding, this study used PLCζ from sheep sperm to construct an early embryonic Ca2+ fluctuation model. First, sheep MII oocytes were cultivated and screened using microinjection technology. Then, a pEGFP-N1-PLCζ plasmid was constructed to activate oocytes in the test group. Ionomycin combined with 6-Dimethylaminopurine (6-DMAP) was used for the control group to explore the effects on early embryonic development and regulation of Ca2+ fluctuations during development. The results demonstrated that both the PLCζ and ionomycin combined with 6-DMAP activation methods induced sheep oocyte parthenogenetic activation and development in early embryos. In comparisons, the cleavage rate of ionomycin combined with 6-DMAP activation was significantly higher than that of PLCζ (60.9% ± 19.4% vs 76.1% ± 0.7%, respectively; p < 0.001), and the blastocyst rates were 16.2% ± 0.62% and 21.1% ± 0.92%, respectively (p < 0.05). Additionally, when comparing the distribution of Ca2+ in early embryos at different stages, Ca2+ in both treatment groups was mainly distributed in the cytoplasm, but the temporal pattern of Ca2+ fluctuations differed. PLCζ resulted in Ca2+ peaks that appeared at the cleavage and morula stages of early embryos, and Ca2+ returned to normal levels at the morula stage. However, the Ca2+ concentration after ionomycin combined with 6-DMAP activation was always much higher than that with PLCζ, and its single peak appeared later than in the PLCζ group. In summary, the PLCζ gene promoted stable regulatory effects on Ca2+ fluctuations at different stages during early embryonic development.

Fully-exposed Pt-Fe cluster for efficient preferential oxidation of CO towards hydrogen purification.

Hydrogen is increasingly being discussed as clean energy for the goal of net-zero carbon emissions, applied in the proton-exchange-membrane fuel cells (PEMFC). The preferential oxidation of CO (PROX) in hydrogen is a promising solution for hydrogen purification to avoid catalysts from being poisoned by the trace amount of CO in hydrogen-rich fuel gas. Here, we report the fabrication of a novel bimetallic Pt-Fe catalyst with ultralow metal loading, in which fully-exposed Pt clusters bonded with neighbor atomically dispersed Fe atoms on the defective graphene surface. The fully-exposed PtFe cluster catalyst could achieve complete elimination of CO through PROX reaction and almost 100% CO selectivity, while maintaining good stability for a long period. It has the mass-specific activity of 6.19 (molCO)*(gPt)-1*h-1 at room temperature, which surpasses those reported in literatures. The exhaustive experimental results and theoretical calculations reveal that the construction of fully-exposed bimetallic Pt-Fe cluster catalysts with maximized atomic efficiency and abundant interfacial sites could facilitate oxygen activation on unsaturated Fe species and CO adsorption on electron-rich Pt clusters to hence the probability of CO oxidation, leading to excellent reactivity in practical applications.

Tuning the selectivity of catalytic nitriles hydrogenation by structure regulation in atomically dispersed Pd catalysts.

The product selectivity in catalytic hydrogenation of nitriles is strongly correlated with the structure of the catalyst. In this work, two types of atomically dispersed Pd species stabilized on the defect-rich nanodiamond-graphene (ND@G) hybrid support: single Pd atoms (Pd1/ND@G) and fully exposed Pd clusters with average three Pd atoms (Pdn/ND@G), were fabricated. The two catalysts show distinct difference in the catalytic transfer hydrogenation of nitriles. The Pd1/ND@G catalyst preferentially generates secondary amines (Turnover frequency (TOF@333 K 709 h-1, selectivity >98%), while the Pdn/ND@G catalyst exhibits high selectivity towards primary amines (TOF@313 K 543 h-1, selectivity >98%) under mild reaction conditions. Detailed characterizations and density functional theory (DFT) calculations show that the structure of atomically dispersed Pd catalysts governs the dissociative adsorption pattern of H2 and also the hydrogenation pathway of the benzylideneimine (BI) intermediate, resulting in different product selectivity over Pd1/ND@G and Pdn/ND@G, respectively. The structure-performance relationship established over atomically dispersed Pd catalysts provides valuable insights for designing catalysts with tunable selectivity.

Regulating coordination number in atomically dispersed Pt species on defect-rich graphene for n-butane dehydrogenation reaction.

Metal nanoparticle (NP), cluster and isolated metal atom (or single atom, SA) exhibit different catalytic performance in heterogeneous catalysis originating from their distinct nanostructures. To maximize atom efficiency and boost activity for catalysis, the construction of structure-performance relationship provides an effective way at the atomic level. Here, we successfully fabricate fully exposed Pt3 clusters on the defective nanodiamond@graphene (ND@G) by the assistance of atomically dispersed Sn promoters, and correlated the n-butane direct dehydrogenation (DDH) activity with the average coordination number (CN) of Pt-Pt bond in Pt NP, Pt3 cluster and Pt SA for fundamentally understanding structure (especially the sub-nano structure) effects on n-butane DDH reaction at the atomic level. The as-prepared fully exposed Pt3 cluster catalyst shows higher conversion (35.4%) and remarkable alkene selectivity (99.0%) for n-butane direct DDH reaction at 450 °C, compared to typical Pt NP and Pt SA catalysts supported on ND@G. Density functional theory calculation (DFT) reveal that the fully exposed Pt3 clusters possess favorable dehydrogenation activation barrier of n-butane and reasonable desorption barrier of butene in the DDH reaction.

Expression and distribution of bone morphogenetic protein 4 and its antagonist Noggin in the skin of Kazakh sheep (Ovis aries) with a white and brown coat color.

The natural coat color is an important trait of vertebrate animals. For example, the coat color can help avoid harm to human beings caused by chemical dyeing, and it has economic significance for domestic animals. The bone morphogenetic protein 4 (BMP4) and its antagonist Noggin can regulate pigmentation and the generation of coat color in mice; thus, they may also regulate the coat color of Kazakh sheep. To gain mechanistic insight into this possibility, we determined the relative expression levels of BMP4 and Noggin in the skin of white and brown Kazakh sheep by quantitative real-time polymerase chain reaction (qPCR) and western blotting analysis. The localization of BMP4 and Noggin were detected by immunohistochemistry (IHC). The results of qPCR and western blot analysis demonstrated that the relative expression levels of BMP4 and Noggin in the skin of brown Kazakh sheep were significantly higher than those in white Kazakh sheep. Our IHC results showed that the BMP4 protein was expressed in the epidermis and root sheath of the Kazakh sheep skin. The Noggin protein was expressed in the epidermis, root sheath, hair shaft, and dermal papilla of the Kazakh sheep skin. These results provide a theoretical basis for additional studies regarding the association and mechanism of BMP4 and Noggin in coat-color formation in Kazakh sheep. These results may provide new methods for developing treatment strategies for pigmentation disorders and diseases.

Highly Selective Aromatization of Octane over Pt-Zn/UZSM-5: The Effect of Pt-Zn Interaction and Pt Position.

The effects of Zn-Pt interaction and Pt dispersion over a uniform compact cylindrical shape ZSM-5 (UZSM-5) on the catalytic octane aromatization performance are investigated. The comparison between different Pt- and Zn-modified ZSM-5 catalysts demonstrates the significance of ZSM-5 morphology and, more importantly, the metal distributions on it. For the UZSM-5 support, Pt atoms prefer to occupy the sites within its inner pores, resulting in high selectivity to xylenes during the octane aromatization. The Zn deposit in inner pores and higher dispersion of Pt lead to the spillover of Pt sites to the external surface, which is critical for the activation of octane to produce reaction intermediates that are further converted to aromatics over the inner pore catalytic sites. These effects are evidenced by a diffuse reflection infrared Fourier transform spectroscopy study of CO adsorbed on the catalyst surface. In situ X-ray absorption fine structure spectra are collected to probe the coordination number and the chemical environment of Pt and Zn atoms in the catalysts during the octane aromatization reaction. Pt and Zn are well dispersed and stable during the reaction, and a partial reduction of Pt during the reaction is observed. A theoretical study using the density functional theory method predicts that the reaction and transition-state intermediates upon octane activation are better stabilized by Pt(111) of Pt external surface sites with a smaller activation barrier, indicating their significance in C-H activation. This hypothesis is further evidenced by comparing the octane aromatization performance of various modified catalysts through varying Zn loading, blocking inner pores, and covering the external catalytic sites with SiO2.

Anchoring Cu1 species over nanodiamond-graphene for semi-hydrogenation of acetylene.

The design of cheap, non-toxic, and earth-abundant transition metal catalysts for selective hydrogenation of alkynes remains a challenge in both industry and academia. Here, we report a new atomically dispersed copper (Cu) catalyst supported on a defective nanodiamond-graphene (ND@G), which exhibits excellent catalytic performance for the selective conversion of acetylene to ethylene, i.e., with high conversion (95%), high selectivity (98%), and good stability (for more than 60 h). The unique structural feature of the Cu atoms anchored over graphene through Cu-C bonds ensures the effective activation of acetylene and easy desorption of ethylene, which is the key for the outstanding activity and selectivity of the catalyst.

Facile synthesis of ECNU-20 (IWR) hollow sphere zeolite composed of aggregated nanosheets.

An ECNU-20 nanosheet zeolite of around 10 nm thickness along the c axis, with a hollow sphere morphology and IWR topology, was synthesized in a germanosilicate system using a commercially available organic amine, 1,8-diazabicyclo[5.4.0]undec-7-ene, as a structure-directing agent. DFT calculations confirmed that a preferential adsorption of these amine molecules took place on the (001) surface, leading to an oriented crystal growth. Moreover, the concentration of the amine determined the aggregation style of these nanosheets.

Application of the dimensional reduction formalism to Pb9-xBax[Li2(P2O7)2(P4O13)2] (x = 0, 2, 6, 7): a series of phosphates with two types of isolated polyphosphate groups.

A series of phosphates, Pb9-xBax[Li2(P2O7)2(P4O13)2] (x = 0, 2, 6, 7), have been synthesized by a high temperature solution method and the crystal structures were determined by single crystal X-ray diffraction. They are isostructural and crystallize in the triclinic space group P1[combining macron]. It is interesting that there are two kinds of isolated polyphosphate anionic groups coexisting in the crystal structure, which is rare among phosphates. Their structures exhibit zero-dimensional [Li2(P2O7)2(P4O13)2]18- anionic clusters constructed by the LiO4, P2O7 and P4O13 groups, which are separated by the Pb2+ or Ba2+ cations. The structure of Pb9[Li2(P2O7)2(P4O13)2] could be obtained using Li2O as a dimensional reduction agent to dismantle Pb3P4O13. In addition, the infrared spectra and the UV-Vis-NIR diffuse reflectance spectra, as well as thermal analyses are reported. The first-principles theoretical studies are also carried out to understand the relationship between their electronic structures and linear optical properties.