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Catalytic upgrading of bio-ethanol to 1,3-butadiene (1,3-BD, ETB) is a renewable and low-carbon technology for the bulk chemical production. Exploring robust catalysts and getting in-depth understanding of the relationship between the structure of catalytic sites and reaction selectivity are of great significance for ETB process applications. In this study, we constructed a robust Cu-Zr/SiO₂ catalyst by an ammonia evaporation and post-impregnation method. Over the optimal 2%Cu-8%Zr/SiO₂ catalyst, superior performance of 69.6% 1,3-BD selectivity and 71.2% ethanol conversion were obtained. Systematic characterizations revealed that three types of Cu-Zr-Si active sites were probably constructed on the Cu-8%Zr/SiO₂ catalysts as varying the Cu loadings from 0.5 to 20%, affording greatly different activity and selectivity in the ETB process. The 1,3-BD productivity over the (SiO)₂(CuO)Zr-OH sites was 8.2 and 77.2 times higher than that of (CuO)₂-Zr-(OSi)₂ and Cu-(O)₂-Zr-(OSi)₂ sites, respectively, attributed to the high activities and good balance among the reactions of dehydrogenation, aldol condensation, and MPVO reduction.

This review provides a comprehensive overview of the distinguished academic career and scientific accomplishments of Prof. Noritatsu Tsubaki at the University of Toyama. For over 35 years, he has dedicated himself to the research field of one-carbon (C1) chemistry, including catalytic conversion of C1 molecules to valuable chemicals and superclean fuels, innovative catalyst and reactor development, and the design of new catalytic reactions and processes. Organized chronologically, this review highlights Prof. Tsubaki's academic contributions from 1990, when he studied and worked at The University of Tokyo, to his current role as a full professor at the University of Toyama. The academic section of this review is divided into three main parts, focusing on Prof. Tsubaki's pioneering work in C1 chemistry. We believe that this review will serve as a highly valuable reference for colleagues in the fields of C1 chemistry and catalysis, and inspire the development of more original and groundbreaking research.

The catalytic performance of different acidic catalysts for diethyl oxalate synthesis from the one-step transesterification of dimethyl oxalate and ethanol was evaluated. The effects of different factors (e.g., acidity, electron accepting capacity, cations type and crystalline water) on the catalytic activity of acidic catalysts were investigated respectively. It was proposed and confirmed that the transesterification reaction catalyzed by a Lewis acid (FeCl₃) and a Bronsted acid (H₂SO₄) follows a first-order kinetic reaction process. In addition, the Lewis acid-catalyzed transesterification processes with different ester structures were used to further explore and understand the speculated reaction mechanism. This work enriches the theoretical understanding of acid-catalyzed transesterification reactions and is of great significance for the development of highly active catalysts for diethyl oxalate synthesis, diminishing the industrial production cost of diethyl oxalate, and developing downstream bulk or high-value-added industrial products.

Red phosphorus has been well-recognized as promising anode materials for lithium-ion batteries (LIBs) and potassium-ion batteries (PIBs) due to its extremely high theoretical capacity and low cost. However, the huge volume change and poor electric conductivity severely limit its further practical application. Herein, the nanoscale ultrafine red phosphorus has been successfully confined in a three-dimensional pitch-based porous carbon skeleton composed of well-interconnected carbon nanosheets through the vaporization-condensation method. Except for the traditional requirement of high electric conductivity and stable mechanical stability, the micropores and small mesopores in the porous carbon matrix centered at 1 to 3 nm and the abundant amount of oxygen-containing functional groups are also beneficial for the high loading and dispersion of red phosphorus. As anode for LIBs, the composite exhibits high reversible discharge capacities of 968 mAh g⁻¹, excellent rate capabilities of 593 mAh g⁻¹ at 2 A g⁻¹, and long cycle performance of 557 mAh g⁻¹ at 2 A g⁻¹. More impressively, as the anode for PIBs, the composite presents a high reversible capacity of 661 mAh g⁻¹ and a stable capacity of 312 mAh g⁻¹ at 0.5 A g⁻¹ for 500 cycles with a capacity retention up to 84.3%. This work not only sheds light on the structure design of carbon hosts with specific pore structure but also open an avenue for high value-added utilization of coal tar pitch.

With the emergence of supercapacitors (SCs), the creation of bio-based electrode materials has grown in significance for the advancement of energy storage. However, it is particularly difficult for cathode materials to meet the demands of practical uses due to their low energy density. Herein, MIL-88 was fabricated in situ on the surface of cotton fibers used in cosmetics, followed by creating Fe₂N@porous carbon fiber composite (Fe₂N@PCF) through heat treatment at various temperatures. Fe₂N@PCF-800 demonstrates excellent specific capacitance performance (552 F g⁻¹ at 1 A g⁻¹). Meanwhile, The AC//Fe₂N@PCF-800 device exhibits the largest energy density of 38 Wh kg⁻¹ at 800 W kg⁻¹ and a long cycling stability (83.3% capacity retention after 6000 cycles). Our elaborately designed Fe₂N@PCF demonstrate multiple advantages: i) the Fe₂N@PCF-800 shows abundant mesopores, providing abundant ion-diffusion pathways for mass transport and rich graphite microstructures, improving electrical conductivity for electron transferowning; ii) the rich nitrogen dopants and Fe₂N structure within all carbon components increase the capacitance through their pseudocapacitive contribution. These findings highlight the importance of biomass derived carbon materials for SCs applications.

The gas-phase hydrogenation of furfural to furfuralcohol over Cr-free Cu-based catalysts has attracted increasing attention due to its environmentally friendly nature and mild operating conditions. Although reduced pure nano-sized CuO exhibits complete furfural hydrogenation and nearly 100% furfuralcohol selectivity, it suffers from rapid deactivation caused by sintering. In this study, we conducted comparative investigations on the catalytic performance and stability of two Cu-based catalysts: 90%CuO-10%SiO₂ and 90%CuO-5%CaO-5%SiO₂, in the gas-phase furfural hydrogenation. The reaction is carried out under various conditions, including temperatures ranging from 120 to 170 ℃, LHSVs of 1 to 2.2 h⁻¹, and H₂ to furfural molar ratios of 3.5 to 12.5. The results indicate that under optimal conditions, the Ca-modified catalyst achieves nearly complete furfural conversion and almost 100% furfuralcohol selectivity for a test duration of 31 h. In contrast, the unmodified catalyst exhibits stable performance for only seven hours despite the similar initial performance. XRD analysis confirms that the gradual deactivation of both catalysts is attributed to the oxidation of reduced metallic Cu sites to Cu oxides. Further characterizations of the two spent catalysts using HRTEM and XPS analyses, along with DFT calculations, suggest that the presence of Ca in Cu lattices prevents the loss of electrons from low-valence Cu sites or the reduced metallic Cu sites, thus inhibiting their oxidation to high-valence Cu oxides. This phenomenon contributes to suppressing the deactivation of Cu-catalysts in the gas-phase furfural hydrogenation process.

With the rapid development of “Internet of Things” and human-computer interaction techniques, it is essential and urgent to develop facile and scalable fabrication platforms for stretchable flexible sensor. Herein, we report a facile strategy of using the green choline chloride–acrylamide deep eutectic solvent (CC-AM DES) to guide the in-situ ring-opening polymerization of α-lipoic acid (LA), leading to the successful development of a stretchable ionogel material. The as-prepared ionogel from CC-AM DES system exhibits multifunctional merits including the super stretchability (>9000%), 100% UV-blocking ability, tunable adhesiveness (29–414 kPa), high ionic conductivity (4.45 × 10⁻⁴ S/cm), and ideal anti-freezing (–27 °C). In addition, this outstanding ionogel can be readily coated on various material substrates with designable shapes and patterns. Owning to these promising properties and performances, a scalable flexible strain sensor is assembled from the ionogel and exhibits stable resistance variations (R/R₀) towards multiple external mechanical stimulus. This study provides a green, cost effective, and scalable strategy to fabricate ionogel materials and multifunctional flexible strain sensors, showing a great potential in the fast-emerging highly stretchable wearable/flexible electronics.

Polyurethane is an excellent and widely used polymer material. In synthesizing polyurethane, the structure of soft and hard segments in polyurethane could be adjusted, which can obtain better properties than other polymer materials, such as good mechanical properties and biocompatibility. In recent years, due to their excellent chemical stability, biocompatibility, and low cytotoxicity, polyurethanes have been widely used for biomedical applications. To solve the problems of degradation and recycling, the development of bio-based polyurethane has also become a current hot spot. This paper summarizes the research progress and applications of polyurethane materials for dressings, skin sensors, orthopedics, and cardiovascular. It also looks forward to the future development of polyurethane medical materials.

Alkaline hydrogen evolution reaction (HER) is suppressed by the water dissociation, leading to more sluggish kinetics than acidic HER. Developing multifunction catalysts via constructing heterogeneous interfaces is a feasible tactic to accelerate the alkaline HER. Herein, NiO coupled with Ni and Mo_xN (NMN) nanorods were prepared via a hydro-thermal synthesis combined with a thermal decomposition under ammonia atmosphere. The low crystalline NMN nanorods are rich in heterointerfaces, and have sufficient high active sites for HER. The synergistic effect between NiO and Ni-Mo_xN promotes the water dissociation the hydrogen adsorption, and the charge transfer, contributing to excellent alkaline HER activity. The overpotential on NMN is only 36 and 150 mV for the current density of 10 and 300 mA cm⁻², respectively, and the Tafel slope is 48 mV/dec, demonstrating a superior performance for alkaline HER, which is even comparable to the commercial electrocatalysts.