Green chemistry

  • Article
    | Open Access

    Inverse vulcanization is a process that enables to convert sulfur, a by-product of the petroleum industry, into polymers. Here the authors report a synthetic method of inverse vulcanization via mechanochemical synthesis; compared to thermal routes, a broader range of monomers can be used, and the protocol yields materials with enhanced mercury capture capacity.

    • Peiyao Yan
    • , Wei Zhao
    •  & Tom Hasell
  • Article
    | Open Access

    Lignin valorization becomes the spotlight on the full utilization of biomass. Here, the authors report a highly dispersed Ru catalyst for reductive catalytic fractionation of lignocellulose, which affords monophenols in theoretical maximum yields, along with high preservation of carbohydrate.

    • Zhenzhen Liu
    • , Helong Li
    •  & Guoyong Song
  • Article
    | Open Access

    Using CO2 as C1-feedstock for the chemical industry has attracted great attention. Here the authors develop a two-step cascade process to perform catalytic carbonylations of olefins, alkynes, and aryl halides using CO2 and H2.

    • Rui Sang
    • , Yuya Hu
    •  & Matthias Beller
  • Article
    | Open Access

    Deuterium-labelled compounds are useful for mechanistic studies and pharmaceutical science, but syntheses are not trivial. Here, the authors report deuteration of unactivated alkyl (pseudo)halides driven by electrochemical force, using deuterium oxide as the source of the isotope.

    • Pengfei Li
    • , Chengcheng Guo
    •  & Youai Qiu
  • Article
    | Open Access

    ‘Polyethylene terephthalate is a widely used polymer with a concerning environmental impact, and alternatives are now highly sought. In this article, the authors present a biorefinery strategy for constructing polyester analogues of polyethylene terephthalate from woody biomass, which are promising candidates for the circular economy.

    • Xianyuan Wu
    • , Maxim V. Galkin
    •  & Katalin Barta
  • Article
    | Open Access

    To solve the serious problem of white plastic pollution many degradation routes are being investigated. Here the authors show a H2-free low-cost Cu/SiO2 catalyzed process to quantitatively convert polyethylene terephthalate into p-xylene and ethylene glycol in one pot with methanol as both the solvent and hydrogen source at 210 °C.

    • Zhiwen Gao
    • , Bing Ma
    •  & Chen Zhao
  • Article
    | Open Access

    CH4 oxidation to high value chemicals under mild conditions through photocatalysis confronts critical issues regarding both conversion and selectivity. Here, atomic Pd and oxygen vacancies were integrated on In2O3 nanorods, leading to visible-driven CH4 conversion with a remarkable yield of oxygenates and high selectivity of primary products.

    • Lei Luo
    • , Lei Fu
    •  & Junwang Tang
  • Article
    | Open Access

    Biomass conversion holds promise as a more sustainable source of platform chemicals, but limitations in the ways in which lignin can be broken down is a current bottleneck. Here the authors report an electrocatalytic hydrogenolysis over skeletal Ni that cleaves diaryl ethers, chemically resistant moieties in both renewable carbon sources and persistent organic pollutants.

    • Yuting Zhou
    • , Grace E. Klinger
    •  & James E. Jackson
  • Article
    | Open Access

    Liquid−liquid transitions (LLTs) have been reported for some molecular systems but are difficult to observe under high pressure conditions. Here the authors report and characterize a first-order LLT in a series of ionic liquids containing the trihexyl(tetradecyl)phosphonium cation and anions of different sizes and shapes, using calorimetric and dielectric measurements.

    • Zaneta Wojnarowska
    • , Shinian Cheng
    •  & Marian Paluch
  • Article
    | Open Access

    As of now, only rule-based systems support retrosynthetic planning using biocatalysis, while initial data-driven approaches are limited to forward predictions. Here, the authors extend the data-driven forward reaction as well as retrosynthetic pathway prediction models based on the Molecular Transformer architecture to biocatalysis.

    • Daniel Probst
    • , Matteo Manica
    •  & Teodoro Laino
  • Article
    | Open Access

    Current recycling methods suffer from harsh reaction conditions and long reaction times. Here the authors show a non-thermal plasma-assisted method for rapid hydrogenolysis of polystyrene at ambient temperature and atmospheric pressure, generating high yield (>40 wt%) of C1–C3 hydrocarbons.

    • Libo Yao
    • , Jaelynne King
    •  & Zhenmeng Peng
  • Article
    | Open Access

    Proteins, other metabolites and many valuable synthetic products contain amide bonds and there is a need for more sustainable amide synthesis routes. Here the authors show an integrated next generation multi-catalytic system, merging nitrile hydratase enzymes with a Cu-catalysed N-arylation reaction in a single reaction vessel, for the construction of ubiquitous amide bonds.

    • Luis Bering
    • , Elliott J. Craven
    •  & Jason Micklefield
  • Article
    | Open Access

    Usually asymmetric hydrogenation of olefins is enantiodivergent and thus requires isomerically pure olefins, which is a considerable drawback. Here, the authors show a general iridium-catalyzed enantioconvergent hydrogenation of a broad range of functionalized trisubstituted olefins.

    • Bram B. C. Peters
    • , Jia Zheng
    •  & Pher G. Andersson
  • Article
    | Open Access

    The recalcitrance of lignocellulosic biomass is the major limitation for the production of natural gas. Here the authors develop a catalytic-drive approach with Ni2Al3 alloy catalyst to enable nearly complete conversion of various agricultural and forestry residues into natural gas.

    • Xiaoqin Si
    • , Rui Lu
    •  & Fang Lu
  • Article
    | Open Access

    Grignard reagents have widespread utility in organic chemistry, but their preparation is limited by several drawbacks, such as the use of dry organic solvents and long reaction times. Here, the authors report a general mechanochemical synthesis of Grignard reagents in paste form in air, using a ball milling technique.

    • Rina Takahashi
    • , Anqi Hu
    •  & Hajime Ito
  • Article
    | Open Access

    Time-resolved in situ (TRIS) X-ray powder diffraction promises great potential to study mechanochemical processes. Here, the authors develop a strategy to enhance the resolution of TRIS experiments to allow deeper interpretation of mechanochemical transformations; the method is applied to a variety of model systems including inorganic, metal-organic, and organic mechanosyntheses.

    • Giulio I. Lampronti
    • , Adam A. L. Michalchuk
    •  & Franziska Emmerling
  • Article
    | Open Access

    Deep eutectic solvents (DES) are intriguing green reaction media for biomass processing, however, undesired lignin condensation is a typical drawback. Here the authors develop a tunable ternary DES system that allows for stabilization of reactive intermediates for efficient lignocellulose fractionation.

    • Yongzhuang Liu
    • , Noemi Deak
    •  & Katalin Barta
  • Article
    | Open Access

    Selective cleavage of C-C bonds is very important in organic chemistry, but remains challenging because of their inert chemical nature. Here, the authors report that Zn2+ coordinated with N species on N-doped carbon catalysts can catalyze the aerobic oxidative cleavage and esterification of C(CO)-C bonds with high efficiency and activity.

    • Chao Xie
    • , Longfei Lin
    •  & Buxing Han
  • Article
    | Open Access

    Single-atom Rh catalysts present superior activity in olefins hydroformylation, yet with limited success in regioselectivity control. Here the authors develop a Rh1 single-atom catalyst with nanodiamond as support, with which good to excellent regioselectivities to branched aldehydes in hydroformylation of terminal olefins are achieved.

    • Peng Gao
    • , Guanfeng Liang
    •  & Fen-Er Chen
  • Article
    | Open Access

    Efficient production of benzene from lignin is attractive and of great importance, but has not been realized. Here, the authors develop a strategy to transform lignin into benzene over a RuW/zeolite catalyst in water, and the yield of benzene can be as high as 18.8% on lignin weight basis.

    • Qinglei Meng
    • , Jiang Yan
    •  & Buxing Han
  • Article
    | Open Access

    For printed electronics to realize its potential as a sustainable ubiquitous technology, eco-friendly solvents that deliver excellent ink performance must be found. Here, the authors report a free online tool that identifies functional green solvents for solution-processed printed electronics.

    • Christian Larsen
    • , Petter Lundberg
    •  & Ludvig Edman
  • Article
    | Open Access

    Compounds bearing a carbonyl group, such as aldehydes and ketones, are important industrial chemicals and widespread in pharmaceuticals and natural products. Here, the authors report a strategy for visible-light photoredox-catalyzed umpolung carboxylation of diverse carbonyl compounds with CO2, to generate valuable α-hydroxycarboxylic acids.

    • Guang-Mei Cao
    • , Xin-Long Hu
    •  & Da-Gang Yu
  • Article
    | Open Access

    The efficiency of chemical reactions in biological systems is often connected to the properties of confined water, but the developments and applications of artificial mimicking systems are impeded by the complexity of the biological systems. Here, the authors show how surface bound water in nanoporous cellulosic fibers can increase the reaction rate of surface acetylation reactions and enable regioselectivity of the reaction

    • Marco Beaumont
    • , Paul Jusner
    •  & Thomas Rosenau
  • Article
    | Open Access

    The scale-up of the coupling of water electroreduction (HER) with organic electrooxidation remains challenging. Here the authors address this challenge by coupling HER with electrooxidation of raw biomass chitin, cogenerating acetate and green hydrogen safely at high current density.

    • Hu Zhao
    • , Dan Lu
    •  & Hong Li
  • Article
    | Open Access

    To date we have a myriad of luminogenes at our deposal but many of them face problems like weakened emission in the aggregated state as well as poor sustainability. Here, the authors develop a class of rosin-derived luminogens with aggregation induced emission properties providing good biocompatibility and demonstrate their application in organelle imaging.

    • Xu-Min Cai
    • , Yuting Lin
    •  & Ben Zhong Tang
  • Article
    | Open Access

    The solar-driven H2 production from water by particulate photocatalysts is an effective approach to produce H2 fuel. Here, the authors propose an integrated photothermal–photocatalytic biphase system, which lowers the reaction barrier and the delivery resistance of the H2, boosting the catalytic H2 evolution rate.

    • Shaohui Guo
    • , Xuanhua Li
    •  & Bingqing Wei
  • Article
    | Open Access

    Organocatalytic atom transfer radical polymerization (O-ATRP) is attractive due to its metal-free nature but catalysts are rarely applied at a low loading. Here the authors introduce a catalyst design logic based on heteroatom-doping of polycyclic arenes, which led to the discovery of oxygen-doped anthanthrene as an organic photoredox catalysts for O-ATRP.

    • Qiang Ma
    • , Jinshuai Song
    •  & Saihu Liao
  • Article
    | Open Access

    Basic ionic liquids provide a buffering effect that enables the efficient synthesis of free formic acid from CO2 hydrogenation. Here, a highly efficient catalytic system that transforms CO2 to formic acid without the need of strong bases is demonstrated, avoiding the formation of formate salts.

    • Andreas Weilhard
    • , Stephen P. Argent
    •  & Victor Sans
  • Article
    | Open Access

    Alcohols are more naturally abundant than carbonyl compounds, which in turn are well known for their reactivity in Grignard reactions. Here, the authors showcase a distinct Grignard-like reactivity by using alcohols as coupling partners with hydrazones and synthesize more complex alcohols under ruthenium catalysis.

    • Chen-Chen Li
    • , Haining Wang
    •  & Chao-Jun Li
  • Article
    | Open Access

    The development of techniques capable of orchestrating the assembly of living cells into multicellular ensembles with synergistic and function is challenge. Here, the authors construct algal or algal/bacterial cells-based core shell-like structure based on aqueous two-phase system for synergic photosynthetic H2 production.

    • Zhijun Xu
    • , Shengliang Wang
    •  & Stephen Mann
  • Article
    | Open Access

    Chiral 1,2-diamines are useful chemicals used as ligands in asymmetric catalysis. Here, the authors report a copper(I)-catalyzed asymmetric α-addition of ketimines derived from trifluoroacetophenone and 2- or 4-NO2-benzylamines to aldimines, affording a series of chiral anti-1,2-diamine derivatives.

    • Xu-Cheng Gan
    • , Cheng-Yuan Zhang
    •  & Liang Yin
  • Article
    | Open Access

    Nitriles are key intermediates in production of pharmaceuticals, agrochemicals and organic materials. Here, the authors report a nickel-catalyzed reductive cyanation of organic chlorides with CO2/NH3 and urea as cyanation reagents to afford a broad range of organic nitriles.

    • Yanan Dong
    • , Peiju Yang
    •  & Yuehui Li
  • Article
    | Open Access

    Transparent wood composites are promising engineered materials for green energy-efficient building. Here, authors demonstrate novel aesthetic wood with integrated functions of optical transparency, UV-blocking, thermal insulation, and mechanical strength for this sustainable application.

    • Ruiyu Mi
    • , Chaoji Chen
    •  & Liangbing Hu