Selective Adsorbent Design with Multifunctional Surfaces: Innovating Solutions for Heterogeneous Catalysis in Water.

Heterogeneous catalytic systems with water as the solvent often have the disadvantage of cross-contamination, while concerns about the purification and workup of the aqueous phase after reactions are rare in the lab or industry. In this context, designing and developing the functional selective solid adsorbent and revealing the adsorption mechanism can provide a new strategy and guidelines for constructing supported heterogeneous catalysts to address these issues. Herein, we report the stable composite adsorbent (Fe/ATP@PPy: magnetic Fe3O4/attapulgite with the polypyrrole shell) that features an integrated multifunctional surface, which can effectively tune the selective adsorption processes for Cu2+, Co2+, and Ni2+ ions and nitrobenzene via the cooperative chemisorption/physisorption in an aqueous system. The adsorption experiments showed that Fe/ATP@PPy displayed significantly higher adsorption selectivity for Ni2+ than Cu2+ and Co2+ ions, especially which exhibited an approximate 100.00% removal for both Ni2+ ions and nitrobenzene in the mixture system with a low concentration. Furthermore, combined tracking adsorption of Ni2+ ions and X-ray photoelectron spectroscopy characterization confirmed that the effective adsorption occurs via ion transfer coordination; the pathway was further validated at the molecular level through theoretical modeling. In addition, the selective adsorption mechanism was proposed based on the adsorption experiment, characterization, and the corresponding density functional theory calculation.

Catalytic dehydrogenative coupling and reversal of methanol-amines: advances and prospects.

The development of efficient hydrogen release and storage processes to provide environmentally friendly hydrogen solutions for mobile energy storage systems (MESS) stands as one of the most challenging tasks in addressing the energy crisis and environmental degradation. The catalytic dehydrogenative coupling of methanol and amines (DCMA) and its reverse are featured by high capacity for hydrogen release and storage, enhanced capability to purify the produced hydrogen, avoidance of carbon emissions and singular product composition, offering the environmentally and operationally benign strategy of overcoming the challenges associated with MESS. Particularly, the cycle between these two processes within the same catalytic system eliminates the need for collecting and transporting spent fuel back to a central facility, significantly facilitating easy recharging. Despite the promising attributes of the above strategy for environmentally friendly hydrogen solutions, challenges persist, primarily due to the high thermodynamic barriers encountered in methanol dehydrogenation and amide hydrogenation. By systematically summarizing various reaction mechanisms and pathways involving Ru-, Mn-, Fe-, and Mo-based catalytic systems in the development of catalytic DCMA and its reverse and the cycling between the two, this review highlights the current research landscape, identifies gaps, and suggests directions for future investigations to overcome these challenges. Additionally, the critical importance of developing efficient catalytic systems that operate under milder conditions, thereby facilitating the practical application of DCMA in MESS, is also underscored.

Flame-Retardant Foamed Material Based on Modified Corn Straw Using Two Nitrogenous Layers.

Foamed materials based on a biopolymer of crop straws are environmentally friendly, but ignitability limits their application. In this study, two nitrogenous layers were introduced onto corn straw by esterification and grafting for flame-retardant purposes. The inner thin nitrogenous layer consisted of imidazole rings, and the outer thick nitrogenous layer consisted of grafted acrylamide by a free-radical polymerization. The outer nitrogenous layer was simultaneously introduced into the system with a foaming process at 150 °C. Azodiisobutyronitrile acted both as initiator of the polymerization and the main foaming agent, and deionized water acted both as a plasticizing agent and an auxiliary foaming agent, which simplified the process and formula. It was found that cavities of two different sizes were formed. The nonuniformity of the foamed material was ascribed to the heterogeneous foaming precursor consisting of a rigid core and a soft shell. Its excellent flame-retard rating of UL-94 V-0 was ascribed to the two nitrogenous layers, which provides a sufficient nitrogen source for non-combustible gases. A relatively high compression strength of 17.7 MPa was partly due to the fiber of corn straw.

In Situ-Generated CuI Catalytic System for Oxidative N-Formylation of N-Heterocycles and Acyclic Amines with Methanol.

The development of a sustainable and simple catalytic system for N-formylation of N-heterocycles with methanol by direct coupling remains a challenge, owing to many competing side reactions, given the sensitivity of N-heterocycles to many catalytic oxidation or dehydrogenation systems. This work concerns the development of an in situ-generated CuI catalytic system for oxidative N-formylation of N-heterocycles with methanol that is based on the case study of a more typical 1,2,3,4-tetrahydroquinoline as substrate. Aside from N-heterocycles, some acyclic amines are also transformed into the corresponding N-formamides in moderate yields. Furthermore, a probable reaction mechanism and reaction pathway are proposed and extension of work based on some findings leads to a demonstration that the formed ⋅O2 - and ⋅OOH radicals in the catalytic system is related to the formation of undesired tar-like products.

Multiple chirality inversion of pyridine Schiff-base cholesterol-based metal-organic supramolecular polymers.

Based on a metal coordination driven co-assembly strategy, a metal-organic supramolecular polymer system of pyridine Schiff-base cholesterol and metal ions with multiple supramolecular chirality inversion was successfully achieved by the stoichiometry and exchange of metal ions (such as Co2+, Ni2+, Cu2+, Zn2+, and Ag+), as well as the solvent polarity.

Preparation of Boron/Sulfur-Codoped Porous Carbon Derived from Biological Wastes and Its Application in a Supercapacitor.

Abundant biomass resources are a good choice for preparing electrode materials for supercapacitors, but developing a versatile and simple synthetic method to convert them into electrode materials remains a challenge. In the present research, our team reports a promising strategy and cost-efficient method to fabricate boron/sulfur-codoped porous carbon from biomass sources, mainly utilizing four biomass materials. Detailed material characterization showed that the samples produced by this approach possess rich B and S doping. Additionally, the original biomass materials treated by activation produce abundant pores. Therefore, owing to the synergetic effect of abundant atomic doping and microporous/mesoporous distribution, the obtained carbon as electrode material manifested excellent specific capacitances of 290 F g-1 at a 0.5 A g-1 current density. Moreover, the specific energy of the prepared samples of the as-assembled symmetric supercapacitor is as high as 16.65 Wh kg-1 in 1 M Na2SO4, with a brilliant cyclical performance of only a 2.91% capacitance decay over 10,000 cycles. In addition, it has been verified universally that three other types of bio-wastes can also prepare electrode material using this method. This paper represents a significant attempt to turn waste biomass into treasure while also providing ideas for the design and preparation of supercapacitor electrode materials.

Preparation and Self-Cleaning Performance of Carbon-Based Superhydrophobic Coatings Based on Non-Fluorine and Non-Toxic Corn Straw.

Recently, superhydrophobic surfaces with self-cleaning ability have attracted broad research interest due to their huge potential in daily lives and industrial applications, but the use of fluorinate, toxic organic compounds, and expensive feedstocks make superhydrophobic materials a great challenge in practical application. In this study, we present a facile dip-coating strategy to prepare superhydrophobic coatings with self-cleaning properties based on a non-fluorine and non-toxic system by using eco-friendly corn straw as raw material. During this process, aromatic carbon particles with rough hierarchical structures were prepared firstly via a simple fast pyrolysis process, followed by modification with polydimethylsiloxane (PDMS) in absolute ethanol solvent to decrease the surface free energy. Research shows these natural straw-derived carbons display a microstructure of several protrusions which is similar to the lotus leave's and the resulted coatings exhibit an outstanding superhydrophobic property with a static water contact angle (WCA) of 151.67 ± 1.36 degrees. In addition, the as-prepared coatings possessed excellent self-cleaning performance: no contaminations were observed on the surfaces after examining with sludge, calcimine, water, and common liquids such as tea, milk, soybean milk as well as ink, which have a broad range of potential application in the field of antifouling, waterproofing, and anticorrosive.

Synthesis of a molecularly defined single-active site heterogeneous catalyst for selective oxidation of N-heterocycles.

Generally, a homogeneous catalyst exhibits good activity and defined active sites but it is difficult to recycle. Meanwhile, a heterogeneous catalyst can easily be reused but its active site is difficult to reveal. It is interesting to bridge the gap between homogeneous and heterogeneous catalysis via controllable construction of a heterogeneous catalyst containing defined active sites. Here, we report that a molecularly defined, single-active site heterogeneous catalyst has been designed and prepared via the oxidative polymerization of maleimide derivatives. These polymaleimide derivatives can be active catalysts for the selective oxidation of heterocyclic compounds to quinoline and indole via the recycling of -C=O and -C-OH groups, which was confirmed by tracing the reaction with GC-MS using maleimide as the catalyst and by FT-IR analysis with polymaleimide as the catalyst. These results might promote the development of heterogeneous catalysts with molecularly defined single active sites exhibiting a comparable activity to homogeneous catalysts.

Synthesis of unsymmetric tertiary amines via alcohol amination.

The first one-pot selective synthesis of unsymmetric tertiary amines is reported by the amination of two types of alcohols with primary amines via the development of a simple CuAlOx-HT catalyst and enables the synthesis of unsymmetric amines in a wide variety of primary amines and alcohols.

Asymmetric zinc-catalyzed hydrosilylation of ketones and the effect of carboxylate on the enantioselectivity.

Several chiral ligands containing (R,R)-diaminocyclohexane moieties and pyrrole, furan, or benzene have been synthesized. These ligands were tested in enantioselective zinc-catalyzed hydrosilylation reactions; excellent enantioselectivities were obtained when the ligands containing (R,R)-diaminocyclohexane moieties and furan rings were used. For comparison, zinc chloride combined with different potassium carboxylate salts and ligands were also tested for catalytic hydrosilylation reactions.