Efficient capture and storage of ammonia in robust aluminium-based metal-organic frameworks.

The development of stable sorbent materials to deliver reversible adsorption of ammonia (NH3) is a challenging task. Here, we report the efficient capture and storage of NH3 in a series of robust microporous aluminium-based metal-organic framework materials, namely MIL-160, CAU-10-H, Al-fum, and MIL-53(Al). In particular, MIL-160 shows high uptakes of NH3 of 4.8 and 12.8 mmol g-1 at both low and high pressure (0.001 and 1.0 bar, respectively) at 298 K. The combination of in situ neutron powder diffraction, synchrotron infrared micro-spectroscopy and solid-state nuclear magnetic resonance spectroscopy reveals the preferred adsorption domains of NH3 molecules in MIL-160, with H/D site-exchange between the host and guest and an unusual distortion of the local structure of [AlO6] moieties being observed. Dynamic breakthrough experiments confirm the excellent ability of MIL-160 to capture of NH3 with a dynamic uptake of 4.2 mmol g-1 at 1000 ppm. The combination of high porosity, pore aperture size and multiple binding sites promotes the significant binding affinity and capacity for NH3, which makes it a promising candidate for practical applications.

Sustainable cellulose-based multifunctional material for electromagnetic shielding, flame retardancy and antibacterial.

Biomass-based multifunctional electromagnetic shielding materials have attracted extensive interest in academia and industry due to the sustainability of biomass and the environmental adaptability of multifunctional materials. After removing lignin and hemicellulose wood become a porous substrate with aligned cellulose, which is a good platform for building cellulose-based materials. In this work, a cellulose composite with sandwich-like structure was constructed by in-situ polymerization of aniline on delignified wood and coating a PDMS/CNT layer. Benefiting from the natural porous hierarchical structure and the constructed multilayer continuous conductive network, the PDMS/CNT/PANI WA exhibits excellent electrical conductivity (18.6 S/m) and electromagnetic shielding performance (shielding efficiency value of 26 dB at the X band (8.2-12.4 GHz)). The synergistic effect of PANI and CNT endowed the material with excellent flame retardancy (HRR, THR and HRC decreased by 84 %, 53.4 % and 83.3 %) and significant antibacterial activity. Moreover, PDMS imparts a water contact angle of 105° to the material, which acts as a protective layer, further improves the durability of the material. This work provides a new strategy for developing sustainable and multifunctional electromagnetic shielding materials.

Bimetallic Aluminum- and Niobium-Doped MCM-41 for Efficient Conversion of Biomass-Derived 2-Methyltetrahydrofuran to Pentadienes.

The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of AlIII and NbV sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure. Operando X-ray absorption, diffuse reflectance infrared and solid-state NMR spectroscopy collectively reveal the molecular mechanism of the conversion of adsorbed 2-MTHF over AlNb-MCM-41. Specifically, the atomically-dispersed NbV sites play an important role in binding 2-MTHF to drive the conversion. Overall, this study highlights the potential of hetero-atomic mesoporous solids for the manufacture of renewable materials.

Superhydrophobic and deacidified cellulose/CaCO3-derived granular coating toward historic paper preservation.

Deacidification and surface self-cleaning are of great significance for the long-term preservation of historic literature. Herein, a superhydrophobic self-cleaning coating, derived from nanocellulose coated with CaCO3 particles is constructed via chemical vapor deposition (CVD) for the first time for the preservation of historic paper. The static contact angle of superhydrophobic paper reached more than 150° and the minimum sliding angle was 6.4°. Deacidification effect was achieved with a desired pH value in the range from 7.50 to 7.77 and the maximum alkali storage was up to 1.235 mol/kg. It is found that the low-cost CaCO3 nanoparticles can not only remove the acid substances, but also gave the paper function of self-cleaning, which is very great significant for the protection of paper-based relics.

Nickel-Catalyzed Thermal Redox Functionalization of C(sp3 )-H Bonds with Carbon Electrophiles.

C(sp3 )-H bond coupling with carbon electrophiles remains rarely explored under thermo-driven hydrogen atom transfer (HAT) conditions due to the challenge of integrating oxidation and reduction in a single operation. We report here a Ni-catalyzed arylation and alkylation of C(sp3 )-H bonds with organohalides to forge C(sp3 )-C bonds by merging economical Zn and tBuOOtBu (DTBP) as the external reductant and oxidant. The mild and easy-to-operate protocol enables facile carbofunctionalization of N-/O-α- and cyclohexane C-H bonds, and preparation of a few intermediates of bioactive compounds and drug derivatives. Preliminary mechanistic studies implied addition of an alkyl radical to a NiII salt.

Bimetallic Aluminum- and Niobium-Doped MCM-41 for Efficient Conversion of Biomass-Derived 2-Methyltetrahydrofuran to Pentadienes.

The production of conjugated C4-C5 dienes from biomass can enable the sustainable synthesis of many important polymers and liquid fuels. Here, we report the first example of bimetallic (Nb, Al)-atomically doped mesoporous silica, denoted as AlNb-MCM-41, which affords quantitative conversion of 2-methyltetrahydrofuran (2-MTHF) to pentadienes with a high selectivity of 91 %. The incorporation of AlIII and NbV sites into the framework of AlNb-MCM-41 has effectively tuned the nature and distribution of Lewis and Brønsted acid sites within the structure. Operando X-ray absorption, diffuse reflectance infrared and solid-state NMR spectroscopy collectively reveal the molecular mechanism of the conversion of adsorbed 2-MTHF over AlNb-MCM-41. Specifically, the atomically-dispersed NbV sites play an important role in binding 2-MTHF to drive the conversion. Overall, this study highlights the potential of hetero-atomic mesoporous solids for the manufacture of renewable materials.

Ni-Catalyzed Cross-Electrophile Coupling of Aryl Triflates with Thiocarbonates via C-O/C-O Bond Cleavage.

A nickel-catalyzed reductive coupling of aryl triflates with thiocarbonates is reported here. Both electron-rich and -deficient aryl C(sp2)-O electrophiles as well as a class of O-tBu S-alkyl thiocarbonates are compatible with the optimized reaction conditions, as evidenced by 49 examples. The reaction also proceeds with good chemoselective cleavage of the C-O bond with regard to thioesters. This work broadens the scope of nickel-catalyzed reductive cross-electrophile coupling reactions.

Zn- and Cu-Catalyzed Coupling of Tertiary Alkyl Bromides and Oxalates to Forge Challenging C-O, C-S, and C-N Bonds.

We describe here the facile construction of sterically hindered tertiary alkyl ethers and thioethers via the Zn(OTf)2-catalyzed coupling of alcohols/phenols with unactivated tertiary alkyl bromides and the Cu(OTf)2-catalyzed thiolation of unactivated tertiary alkyl oxalates with thiols. The present protocol represents one of the most effective unactivated tertiary C(sp3)-heteroatom bond-forming conditions via readily accessible Lewis acid catalysis that is surprisingly less developed.

Cellulose nanocrystal mediated fast self-healing and shape memory conductive hydrogel for wearable strain sensors.

Electro-conductive hydrogel (ECH) with self-healing, shape memory and biocompatible properties is highly urgent for wearable strain sensors to prolonging their lifespan, endowing programmable shape control property, and improving affinity to skin during service. However, most of synthetic polymer-based ECH usually involve potential toxicity, long healing and shape drive time. Herein, a fast healable and shape memory ECH with excellent biocompatibility is reported for the first time by incorporating cellulose nanocrystals grafted phenylboronic acid (CNCs-ABA) and multiwalled carbon nanotubes (MWCNTs) into polyvinyl alcohol (PVA). CNCs-ABA is designed as dispersant and crosslinker in hydrogel. pH-induced dynamic borate bonds give hydrogel excellent shape recovery and fixity ratio of 82.1% and 78.2%, respectively. Meanwhile, 97.1% healing efficiency is obtained within 2 min depending on remarkable photothermal effect of MWCNTs and reversible microcrystallization. Double crosslinking networks endow excellent mechanical properties to hydrogel, whose tensile strength, strain and elastic modulus reach 227.0 kPa, 395.0% and 9.0 kPa, respectively. Furthermore, the synergistic effect of MWCNTs and NaOH enhance the conductivity of hydrogel with value of 3.8×10-2 S/m. In addition, the hydrogel can act as strain sensor for detecting human motion with superior biocompatibility and fast resistance response to applied strain, which is suitable for human health management.

Structural reconstruction strategies for the design of cellulose nanomaterials and aligned wood cellulose-based functional materials - A review.

Cellulose is the world's most abundant natural polymer that displays highly desirable characteristics such as biodegradability and sustainability. Its derivatives and associated structured functional materials have potential in various fields such as surface engineering, energy and storage, water treatment, flexible electronics, construction, physical protection, and optical components. All of these applications demand nanocellulose-based micro/nano structural reconstruction for high performance. Recently, functional materials based on aligned nanocellulose in wood obtained through a top-down strategy have highlighted the importance of structure reconstruction strategies on functional designs. In this review, various cellulose or wood micro/nano materials designed by structure reconstruction were examined to highlight the importance of structure reconstruction strategies for various functionalities.

Dialdehyde cellulose nanocrystals act as multi-role for the formation of ultra-fine gold nanoparticles with high efficiency.

Gold nanoparticles (AuNPs) within 10 nm prepared and stabilized by environmentally friendly reducing and supporting agents are highly desired to obtain excellent catalytic properties for organic transformation. In this paper, a rapid and mild strategy for synthesizing ultra-fine AuNPs is reported by using dialdehyde cellulose nanocrystals (DACNCs) as both efficient reductant, dispersant and template for the first time. DACNCs with higher content of aldehyde groups, acting as multi-role player, are crucial to limit the size of AuNPs within 10 nm. Furthermore, AuNPs with average diameter of 5.1 ± 1.0 nm are quantitative obtained at ambient temperature by reducing chloroauric acid within 1 h under conditions of pH= 10.8, 53% aldehyde content, 0.4% DACNCs and 0.25 mM gold ions. In addition, a quantitative method for monitoring the exhaustion of gold ions is established to clarify the synthetic mechanism of AuNPs. Finally, reduction of 4-nitrophenol under AuNPs catalysis is conducted to verify the superiority of as-prepared ultra-fine AuNPs.

A cellulose nanoarchitectonic: Multifunctional and robust superhydrophobic coating toward rapid and intelligent water-removing purpose.

The present work deals with using thermal aggregation of spray drying to achieve uniform structuring of cellulose nanocrystals (CNC) with carbon nanotubes (CNT), for obtaining rough annular microparticles with hierarchical dual dimensions. The structure and characteristics of CNC are crucial to microparticle assembly and superhydrophobic modification. The polyurethane (PU) was used to enhance the firmness of microparticles, during thermal aggregation. The investigated CNC/CNT/PU microparticles showed excellent separation ability for water-in-oil emulsions. Moreover, an abrasion-resistant superhydrophobic coating that combined fast and intelligent water-removing, electrical-conductive and antibacterial functions was manufactured through simple spray coating, which profited from effective role of CNT in excellent conversion of light to heat, as well as its thermal, electrical conductivity and antibacterial properties.

High-value utilization of hydroxymethylated lignin in polyurethane adhesives.

Lignin is a good candidate for the polymerization and chemical modification to prepare sustainable chemicals and materials, but a relatively low hydroxyl content becomes an obstacle for the preparation of lignin-based polyurethane (PU) adhesives. In order to improve its reactivity, the acetic acid lignin (AAL) was hydroxymethylated before copolymerized with isocyanate during the preparation of PU adhesives. The hydroxymethylation was carried out in an alkaline formaldehyde solution and it was found that 85 °C is the optimal temperature. On that condition, the free formaldehyde content of the corresponding product HL-6 was as low as 0.32%, while the hydroxymethyl was increased by 189.11% compared with original AAL and reached 2.92 mmol/g. In the polymerization of PU adhesives, the hydroxymethylated lignin with a higher aliphatic hydroxyl content formed a more compact three-dimensional urethane cross-linking network with isocyanate. The mechanical properties and thermal stability of the lignin-based PU adhesive were improved by 15-30 wt% in HL-6, and particularly the tensile strength was increased by 21-41 MPa, which indicated that the hydroxymethylation is an efficient way to enrich the hydroxyl in lignin, and the modified lignin is adequate to partially replace petroleum-based polyols for the preparation of PU adhesives with excellent properties.