Industrial Chemistry & Materials最新文献

The oxygen evolution reaction (OER) represents an anodic reaction for a variety of sustainable energy conversion and storage technologies, such as hydrogen production, CO₂ reduction, etc. To realize the large-scale implementation of these technologies, the sluggish kinetics of the OER resulting from multi-step proton/electron transfer and occurring at the gas–liquid–solid triple-phase boundary needs to be accelerated. Manganese oxide-based (MnO_x) materials, especially MnO₂, have become promising non-precious metal electrocatalysts for the OER under acidic conditions due to the good trade-off between catalytic activity and stability. This paper reviews the recent progress of MnO₂-based materials to catalyze the OER through either the traditional adsorbent formation mechanism (AEM) or the emerging lattice-oxygen-mediated mechanism (LOM). Pure manganese dioxide OER catalysts with different crystalline structures and morphologies are summarized, while MnO₂-based composite structures are also discussed, and the application of MnO₂-based catalysts in PEMWEs is summarized. Critical challenges and future research directions are presented to hopefully help future research.

Keywords: Manganese dioxides; Electrocatalysts; Oxygen evolution reaction; Adsorbate evolution mechanism; Lattice-oxygen-mediated mechanism.

Layered double hydroxides (LDHs) are regarded as ideal materials for supercapacitors due to their excellent electrochemical characteristics and unique structural properties. However, unsatisfactory cyclability and poor conductivity have been recognized as the key limitations to LDH performance. To overcome these obstacles, constructing hybrid materials as well as designing porous nanoarchitectures are efficient approaches. Herein, through controlling the sulfide ion concentration during the synthesis of CuS nanosheets and adjusting the amount of urea in the synthesis of flower-like ZnCo-LDH structures, an optimized sample with an exclusive porous texture was fabricated on nickel foam (NF) (identified as NF@CS10-ZC-LDH4) via two-step hydrothermal routes and then employed as a binder-less electrode for a hybrid supercapacitor. The as-fabricated nanoarchitectures provide efficient electron-ion transport channels and preserve the structural integrity during prolonged periods of cycling, which resulted in fantastic supercapacitive properties with a capacity of 1270.5 C g⁻¹ and excellent cyclability (remaining at 90.7% after 7000 cycles). Furthermore, we fabricated a hybrid supercapacitor (NF@CS10-ZC-LDH4//NF@AC) with NF@CS10-ZC-LDH4 as a cathode electrode and activated carbon (AC)-covered NF as an anode electrode. The energy density of NF@CS10-ZC-LDH4//NF@AC was high, at 62.4 W h kg⁻¹ with a power density of 810.4 W kg⁻¹ and splendid cyclability of 88.4%. This innovative study offers valuable inspiration for the synthesis of electrode materials to be used in hybrid supercapacitors.

Keywords: Layered double hydroxides; Flower-like ZnCo-LDH; Hybrid supercapacitors; CuS nanosheets.

Proton exchange membrane fuel cells (PEMFCs) have great potential to become the next generation green energy technique, but their application is limited by the slow kinetics of the cathode oxygen reduction reaction (ORR) in acidic medium. Meanwhile, the high price of Pt-based catalysts, which are now widely used commercially, has raised the cost of PEMFCs. Therefore, non-noble metal ORR catalysts as alternatives to Pt-based group metals (PGM) have attracted much attention. However, there is still a big gap between the performance of non-noble metal catalysts and commercial Pt/C catalysts in acidic environment. Recently, it has been realized that the performance of catalysts is closely related to the structure of catalytically active sites. Inspired by this, in this review, we firstly introduced the development and breakthrough of non-noble metals as activity sites. We then briefly summarized their catalytic mechanisms, and put forward some suggestions on how to improve the activity and stability of non-noble metal ORR catalysts.

Keywords: ORR; Non-noble metal single atom catalysts; Active site; Fuel cell.

In recent decades, the use of 1,3-butadiene as a comparably cheap and abundant raw material for new applications has attracted more and more interest, specifically in the chemical industry. The present review covers several of the most important homogeneously catalyzed processes and technologies which are currently used or have the potential to produce fine and bulk chemicals from 1,3-butadiene. As an example, palladium-catalyzed telomerizations provide valuable chemicals through the selective dimerization of 1,3-dienes with the simultaneous addition of various nucleophiles, which can be used for the synthesis of 1-octene, 1-octanol, and various lactones. On the other hand, direct carbonylation allows the selective introduction of functional groups onto 1,3-dienes, such as carbonyl, carboxyl or ester groups. The key to success in achieving these industrially relevant conversions of 1,3-butadiene was mainly the development of innovative efficient catalysts. We hope this review will make readers familiar with the industrially applied and relevant transformations of 1,3-butadiene and inspire them to further explore new and advanced systems.

Keywords: 1,3-Butadiene; Industrial chemistry; Carbonylation reaction; Bulk chemicals; Telomerization.

The Haber–Bosch process is the dominant approach for NH₃ production today, but the process has to be maintained at energy-intensive high temperatures and pressures. Li-mediated electrocatalytic dinitrogen reduction reaction (eN₂RR) could instead enable sustainable and green NH₃ production at ambient conditions. Lithium mediators realize the synthesis of NH₃via the formation of Li₃N, and thus lower the energy required for the direct cleavage of N₂. There has now been a surge of interest in devising approaches to optimize the NH₃ yield rate and faradaic efficiency of the eN₂RR process by employing different catalysts as well as electrolytes. This review discusses the recent advances in the field of the Li-mediated eN₂RR along with the latest insights into the proposed catalytic mechanisms. Moreover, it also highlights the state-of-the-art reported electrocatalysts and electrolytes that have revolutionized the field of the Li-mediated eN₂RR. In addition to the above, our review provides a critical overview of certain limitations and a future prospectus that will provide a way forward to explore this area.

Keywords: Nitrogen reduction reaction; Ammonia; Electrocatalysis; Lithium; Reaction mechanism.

The present contribution emphasizes the formation of oligomeric products in various depolymerization approaches of lignin, namely reductive catalytic fractionation, oxidative catalytic fractionation, and pyrolysis. Three possible routes to form such oligomers in these depolymerization processes are summarized and compared from various studies conducted on model compounds. Next, the main identification techniques for characterizing oligomeric products are highlighted. Particular focus is given to 2D-HSQC-NMR, GPC, Maldi-TOF-MS and FT-ICR-MS, which represent the state-of-art characterization of lignin. Special attention was paid to the transferability of these techniques for depolymerized oligomeric lignin. Finally, both the existing and expected potential lignin valorization routes are discussed for these oligomers, and technical hurdles and recommendations are provided in an attempt to catalyze the development of new discoveries and enabling technologies.

Keywords: Lignin oligomer; Reductive and oxidative depolymerization; Biofuels; Characterization techniques; Lignin valorization.

Correction for ‘Hierarchically ordered porous carbon with atomically dispersed cobalt for oxidative esterification of furfural’ by Wen Yao et al., Ind. Chem. Mater., 2023, 1, 106–116, https://doi.org/10.1039/D2IM00045H.

The implementation of synthetic polymer membranes in gas separations, ranging from natural gas sweetening, hydrogen separation, helium recovery, carbon capture, oxygen/nitrogen enrichment, etc., has stimulated the vigorous development of high-performance membrane materials. However, size-sieving types of synthetic polymer membranes are frequently subject to a trade-off between permeability and selectivity, primarily due to the lack of ability to boost fractional free volume while simultaneously controlling the micropore size distribution. Herein, we review recent research progress on microporosity manipulation in high-free-volume polymeric gas separation membranes and their gas separation performance, with an emphasis on membranes with hourglass-shaped or bimodally distributed microcavities. State-of-the-art strategies to construct tailorable and hierarchically microporous structures, microporosity characterization, and microcavity architecture that govern gas separation performance are systematically summarized.

Keywords: Gas separation membranes; Hierarchical microporosity; Micropore size distribution; Configurational free volume; Solution–diffusion mechanism.

Organic materials with room-temperature phosphorescence (RTP) emission have attracted extensive attention owing to their extraordinary properties, including long lifetime, large Stokes shift, and stimuli-responsiveness, and show bright prospects in broad fields. Numerous design strategies, such as creating a rigid environment through crystallization and supramolecular assembly, can be employed to improve the luminescent characteristics of RTP materials by restricting nonradiative transition, enhancing intersystem crossing, and so forth. This review summarizes recent progress with organic room-temperature phosphorescent materials from the perspective of practical applications, including luminescence and display, environmental detection, and bioimaging, and the challenges and prospects will be discussed at the end, which should assist with future research on the application of RTP materials.

Keywords: Room-temperature phosphorescence; OLEDs; Anti-counterfeiting; Environmental detection; Bioimaging.

Ionic skin, as an emerging subclass of artificial skin, has been proposed and developed for nearly a decade, which makes up for the partial shortcomings of electronic skin to some extent. Highly similar to the ion-sensing mechanism of natural skin, the ionic skin also acquires and conducts perceptual signals in the form of ions. During this decade, a great deal of effort has been devoted to the species amplification of ionic soft matter and the discovery of new mechanisms of artificial ion sensing. It is worth emphasizing that the deciphering of the perceptual mechanisms of natural skin has inspired a great number of bionic studies in pursuit of the reproduction of natural touch in ionic skin. Ionic skin, as a multi-functional operating platform, is also endowed with attractive functions that are beyond natural skin. The birth and appearance of ionic skin greatly promote the vigorous development of products in the era of the internet of things, such as human-machine interaction, prosthetics and wearable devices. In this review, on the basis of explaining the perceptual mechanism of natural skin, we deeply analyze the progressive sensing mechanism of bionic ionic skin. The typical cases of ionic skin that are beyond the ability of natural skin are also summarized in detail. Finally, constructive perspectives and common issues are presented for the future development of ionic skin.

Keywords: Ionic skin; Tactile perception; Bionic; Flexible sensor.