This review discusses the prospect of utilizing earth-abundant CO₂ as a feedstock for value-added chemicals via hydrogenation reaction. The recent progress of CO₂ mitigation strategies using solid-supported catalysts and its opportunities for converting to numerous value-added chemicals, such as olefin, methanol, and formic acid, are discussed.

Abstract

Reducing CO₂ emissions is an urgent global priority. In this context, several mitigation strategies, including CO₂ tax and stringent legislation, have been adopted to halt the deterioration of the natural environment. Also, carbon recycling procedures undoubtedly help reduce net emissions into the atmosphere, enhancing sustainability. Utilizing Earth's abundant CO₂ to produce high-potential green chemicals and light fuels opens new avenues for the chemical industry. In this context, many attempts have been devoted to converting CO₂ as a feedstock into various value-added chemicals, such as CH₄, lower methanol, light olefins, gasoline, and higher hydrocarbons, for numerous applications involving various catalytic reactions. Although several CO₂-conversion methods have been used, including electrochemical, photochemical, and biological approaches, the hydrogenation method allows the reaction to be tuned to produce the targeted compound without significantly altering infrastructure. This review discusses the numerous hydrogenation routes and their challenges, such as catalyst design, operation, and the combined art of structure-activity relationships for the various product formations.

Contrasting mechanical property and surface wettability of the single crystals of concomitant dimorphs of a well-known mesogen n-octyloxybenzoic acid is discovered, and structure-property correlation is established.

Abstract

4-n-octyloxy benzoic acid is known to exhibit liquid crystalline properties, and under normal pressure and temperature conditions, it exists as at least two crystalline polymorphs. We revisited the system and discovered that single crystals of one of the polymorphs display plastic deformation, whereas the other is brittle. n-octyl chains are arranged in an end-to-end fashion, forming slip planes in the plastically deformable polymorph, whereas they are interdigitated in the crystal structure of the brittle polymorph. Due to the difference in the arrangement of the −COOH group and alkyl chains, the major faces of the crystals of both polymorphs possess significant differences in the wettability towards moisture.

A selective and stable hydrogenation of EL to diol is achieved over a bifunctional Co/CoO catalyst derived from CoAl−LDH, where the synergetic catalysts are found to promote the hydrogenation at the unique Co/CoO interfacial structure with the activation of H₂ on metallic Co⁰ and strong adsorption of EL via hydroxyl groups over CoO site.

Abstract

The development of effective and stable non-precious catalysts for hydrogenation of ester to diols remains a challenge. Herein, the catalytic hydrogenation of ethyl lactate (EL) to 1,2-propanediol (1,2-PDO) with supported Co catalysts derived from layered double hydroxides (LDHs) is investigated. Catalytic tests reveal that LDH-derived Co catalysts exhibit the best catalytic performance with 98 % of EL conversion and >99 % of 1,2-PDO selectivity at mild conditions, compared with other Co catalysts (supported on Al₂O₃, and TiO₂) and LDH-derived Cu catalysts. Due to the strong interaction among Co and Al matrix, the main composition is metallic Co⁰ and CoO after reduction at 600 °C. Besides, the catalyst shows good recyclability in the liquid phase hydrogenation. The superior catalytic performance can be attributed to the synergistic effect between Co⁰ and CoO, in which H₂ molecule is activated on Co⁰ and EL is strongly adsorbed on CoO via hydroxyl groups.

Several new mixed ligand diorganotin complexes, [(n-Bu₂SnL¹⁻³)₂SO₄] and [(Me₂Sn)₂(L²)₃(OSO₂Me)] (HL= quinadic acids) have been synthesized and structurally characterized by X-ray crystallography.

Abstract

The synthesis of mixed ligand di-n-butyltin complexes, [(n-Bu₂SnL¹⁻³)₂SO₄], 2–4 (HL¹⁻³=2-quinoline/ 1-isoquinoline/ 4-methoxy-2-quinoline carboxylic acid) has been realized by reacting n-Bu₂Sn(OMe)OSO₂Me, 1 a with the corresponding quinaldic acid under solvothermal conditions. The observed transformation of methane sulfonate to sulfate anion represents a rare example of C−S bond cleavage on the organotin scaffolds, n-Bu₂Sn(L¹⁻³)OSO₂Me, which have been identified as en route intermediates by NMR and X-ray crystallography. Analogous reaction when extended with Me₂Sn(OMe)OSO₂Me, 1 b and HL² yields [(Me₂Sn)₂(L²)₃(OSO₂Me)], 5 as partially disproportionated product of Me₂Sn(L²)OSO₂Me. The solid-state structures of 2–5 reveal variable modes of coordination of the ligands to afford molecular and polymeric motifs.

The antioxidant power of quercetin-3-O-glucuronide (miquelianin) has been studied, at the density functional level of theory, in both lipid-like and aqueous environments. In the aqueous phase, the computed pKa equilibria allows the identification of the neutral and charged species present in solution that can react with the •OOH radical. The Hydrogen Atom Transfer (HAT), Single Electron Transfer (SET) and Radical Adduct Formation (RAF) mechanisms were considered and the individual, total and fraction corrected total rate constants were obtained. Potential non covalent inhibition of Mpro from SARS-CoV-2 by miquelianin has been also been evaluated.

This review provides recent progress on the machine learning-assisted design synthesis of optoelectronic materials and beyond for electroluminescent light-emitting diodes applications, including the introduction of the basic process of the machine learning method, strategy of developing appropriate descriptors and the discovered candidate materials for high-performance devices.

Abstract

Optoelectronic devices, such as light-emitting diodes, have been demonstrated as one of the most demanded forthcoming display and lighting technologies because of their low cost, low power consumption, high brightness, and high contrast. The improvement of device performance relies on advances in precisely designing novelty functional materials, including light-emitting materials, hosts, hole/electron transport materials, and yet which is a time-consuming, laborious and resource-intensive task. Recently, machine learning (ML) has shown great prospects to accelerate material discovery and property enhancement. This review will summarize the workflow of ML in optoelectronic materials discovery, including data collection, feature engineering, model selection, model evaluation and model application. We highlight multiple recent applications of machine-learned potentials in various optoelectronic functional materials, ranging from semiconductor quantum dots (QDs) or perovskite QDs, organic molecules to carbon-based nanomaterials. We furthermore discuss the current challenges to fully realize the potential of ML-assisted materials design for optoelectronics applications. It is anticipated that this review will provide critical insights to inspire new exciting discoveries on ML-guided of high-performance optoelectronic devices with a combined effort from different disciplines.

The schematic illustrates the separation mechanism of pGO membranes. The L-pGO membrane, with extended interlayer mass transfer paths, regular pores, and abundant in-plane defects, exhibits superior permeability. In contrast, the S-pGO membrane, with shorter paths and fewer in-plane defects, excels in dye rejection.

Abstract

Graphene Oxide (GO) membrane has been extensively applied in the field of water purification and membrane separation processes. While the solute molecule transport in GO membranes encompasses interlayer channels, edge defects, and in-plane crack-like holes, the significance of edge defects or crack-like pores in ultrathin membranes is often overlooked. In our study, we focused on the construction of short-range channel GO membranes with varied defect structures by modulating the transverse size of the porous nanosheets. GO nanosheets with different sizes were procured through high-energy γ-irradiation combined with centrifugation. Notably, the large-sized porous GO nanosheets (L-pGO) exhibit a consistent structure, and numerous in-plane defects. In contrast, the smaller counterparts (S-pGO) present a fewer in-plane defects. The performance metrics revealed that L-pGO exhibited a water flux of 849.25 L m⁻² h⁻¹ bar⁻¹, while S-pGO demonstrated nearly 100 % dye rejection capacity. These findings underscore the potential of defect engineering as a powerful strategy to enhance the efficiency of two-dimensional membranes.

This study explores veralipride, a benzamide-class antipsychotic and dopamine D2 receptor antagonist, for its inhibitory effects on carbonic anhydrase (CA) isoforms. In vitro profiling reveals potent inhibition across hCA I, II, and CA XII. In addition, X-ray crystal structure experiments of veralipride adducts with hCA I, II, and CA XII mimic elucidates molecular interactions, aiding in designing polypharmacological compounds.

Abstract

The inhibitory effects of veralipride, a benzamide-class antipsychotic acting as dopamine D₂ receptors antagonist incorporates a primary sulfonamide moiety and was investigated for its interactions with carbonic anhydrase (CA) isoforms. In vitro profiling using the stopped-flow technique revealed that veralipride exhibited potent inhibitory activity across all tested hCA isoforms, with exception of hCA III. Comparative analysis with standard inhibitors, acetazolamide (AAZ), and sulpiride, provided insights for understanding the relative efficacy of veralipride as CA inhibitor. The study reports the X-ray crystal structure analysis of the veralipride adduct with three human (h) isoforms, hCA I, II, and CA XII mimic, allowing the understanding of the molecular interactions rationalizing its inhibitory effects against each isoform. These findings contribute to our understanding of veralipride pharmacological properties and for the design of structural analogs endowed with polypharmacological properties.

Spontaneous coalescence, prone oxidizability, and deterioration in photothermal conversion of liquid metal (LM) impeded the potential application as photothermal agent. Herein, a new surface engineering strategy for LM was developed by implementing self-polymerization of biomimetic polydopamine armor on eutectic gallium-indium-tin ternary alloy, a typical low melting point gallium-based LM alloy.liquid metalsurface engineeringpolydopaminephotothermal conversionphotothermal stability

Abstract

Liquid metal (LM) faces numerous obstacles like spontaneous coalescence, prone oxidizability, and deterioration in photothermal conversion, impeding the potential application as photothermal agent. To tackle these issues, several studies have focused on surface engineering strategy. Developing a feasible and efficient surface engineering strategy is crucial to prevent the aggregation and coalescence of LM, while also ensuring exceptional photothermal conversion and biosecurity. In order to achieve these goals in this work, the biomimetic polydopamine (PDA) armor was chosen to encase a typical LM (eutectic gallium-indium-tin alloy) via self-polymerization. Characterization results showed that the PDA encased LM nanoparticle exhibited enhanced photothermal stability, photothermal conversion, and biosecurity, which could be derived from the following factors: (1) The PDA protective shell acted as an “armor”, isolating LM from dissolved oxygen and water, inhibiting heating-accelerated oxidation and shape morphing. (2) The exceptional near-infrared absorption of PDA was conducive to the photothermal conversion. (3) The biomimetic characteristic of polydopamine (PDA) was advantageous for improving the biosecurity. Hence, this work presented a new surface engineering strategy to reinforce LM for photothermal conversion application.

Downconverted and upconverted emission are mechanochemically activated by ultrasound, compression and freezing, respectively, in polymers incorporated with a Diels-Alder adduct mechanophore that releases 9-styrylantharene chromophores when force is applied.

Abstract

Fluorescent mechanophores can indicate the deformation or damage in polymers. The development of mechanophores with multi-triggered response is of great interest. Herein, Diels-Alder (DA) adducts are incorporated into linear poly(methyl acrylate) PMA-BA and network poly(hexyl methacrylate) (PHMA) as mechanophores to detect the stress caused by ultrasound, freezing, and compression. The DA mechanophores undergo retro-DA reaction to release 9-styrylanthracene chromophore upon applying force, resulting in cyan fluorescence. The dissociation ratio of the DA mechanophore after pulsed ultrasonication of PMA-BA solution for 240 minutes is estimated to be 52 % by absorption spectra and ¹H NMR. Additionally, the rate constant of mechanical cleavage is calculated to be 1.2×10⁻⁴ min⁻¹⋅kDa⁻¹ with the decrease in molecular weight from 69 to 22 kDa measured by gel permeation chromatography. Freezing of PHMA gels as well as compression of PHMA bulk samples turn-on the DA mechanophores, revealing the microscale fracture. Photon upconversion responses toward various force stimuli are also achieved in both polymer solutions and bulk samples by doping platinum octaethylporphyrin (PtOEP) or palladium meso-tetraphenyltetrabenzoporphyrin (PdTPTBP) sensitizers with multiple excitation wavelengths.