Upcycling of polyethylene to gasoline through a self-supplied hydrogen strategy in a layered self-pillared zeolite.

Conversion of plastic wastes to valuable carbon resources without using noble metal catalysts or external hydrogen remains a challenging task. Here we report a layered self-pillared zeolite that enables the conversion of polyethylene to gasoline with a remarkable selectivity of 99% and yields of >80% in 4 h at 240 °C. The liquid product is primarily composed of branched alkanes (selectivity of 72%), affording a high research octane number of 88.0 that is comparable to commercial gasoline (86.6). In situ inelastic neutron scattering, small-angle neutron scattering, solid-state nuclear magnetic resonance, X-ray absorption spectroscopy and isotope-labelling experiments reveal that the activation of polyethylene is promoted by the open framework tri-coordinated Al sites of the zeolite, followed by ß-scission and isomerization on Brönsted acids sites, accompanied by hydride transfer over open framework tri-coordinated Al sites through a self-supplied hydrogen pathway to yield selectivity to branched alkanes. This study shows the potential of layered zeolite materials in enabling the upcycling of plastic wastes.

Nanoparticles and single atoms of cobalt synergistically enabled low-temperature reductive amination of carbonyl compounds.

Low-temperature and selective reductive amination of carbonyl compounds is a highly promising approach to access primary amines. However, it remains a great challenge to conduct this attractive route efficiently over earth-abundant metal-based catalysts. Herein, we designed several Co-based catalysts (denoted as Co@C-N(x), where x represents the pyrolysis temperature) by the pyrolysis of the metal-organic framework ZIF-67 at different temperatures. Very interestingly, the prepared Co@C-N(800) could efficiently catalyze the reductive amination of various aldehydes/ketones to synthesize the corresponding primary amines with high yields at 35 °C. Besides non-noble metal and mild temperature, the other unique advantage of the catalyst was that the substrates with different reduction-sensitive groups could be converted into primary amines selectively because the Co-based catalyst was not active for these groups at low temperature. Systematic analysis revealed that the catalyst was composed of graphene encapsulated Co nanoparticles and atomically dispersed Co-N x sites. The Co particles promoted the hydrogenation step, while the Co-N x sites acted as acidic sites to activate the intermediate (Schiff base). The synergistic effect of metallic Co particles and Co-N x sites is crucial for the excellent performance of the catalyst Co@C-N(800). To the best of our knowledge, this is the first study on efficient synthesis of primary amines via reductive amination of carbonyl compounds over earth-abundant metal-based catalysts at low temperature (35 °C).

A bright chemiluminescence conjugated polymer-mesoporous silica nanoprobe for imaging of colonic tumors in vivo.

Hypochlorite acid (ClO-) is one of the major reactive oxygen species (ROS) in colon cancer, providing an effective target for colonic tumor in vivo imaging. For detection of ClO- and tumor imaging, poly[(9,9-di(2-ethylhexyl)-9H-fluorene-2,7-vinylene)-co-(1-methoxy-4-(2-ethylhexyloxy)-2,5-phenylenevinylene)] (PFV-co-MEHPV, namely CP1) was encapsulated in mesoporous silica nanoparticles (MSNs) that were pre-modified with polyphenylenevinylene (PPV) via in situ polymerization to construct bright PPV@MSN-CP1 nanoparticles. The synthesized nanoparticles were size-stable and not cytotoxic as confirmed by FE-TEM, FE-SEM, and MTT assay. Hypochlorite oxidizes the vinylidene bond of CP1 through π2-π2 cycloaddition to form PPV-dioxetane intermediates to generate photons. The CL quantum yield of PPV@MSN-CP1 was 16.7 times higher than that of Pluronic F-127 wrapped CP1. CL nanoparticles PPV@MSN-CP1 have good selectivity for hypochlorite detection among biological oxidants (mainly ROS). The linear range and the LOD of PPV@MSN@CP1 for ClO- detection are 4-90 and 1.02 µM, respectively. Subsequently, we further coated PPV@MSN@CP1 with folic acid for tumor targeting by phospholipid wrapping. PPV@MSN-CP1@FA was successfully applied for in vivo imaging of endogenously produced ClO- of tumor tissue in living animals.

Stable SERS substrate based on highly reflective metal liquid-like films wrapped hydrogels for direct determination of small molecules in a high protein matrix.

The study of the interaction between small molecules and proteins is important. Surface-enhanced Raman spectroscopy (SERS) is suitable for such applications since it has the power of detecting a molecule based on its intrinsic nature and without labeling. Herein, the MeLLFs@PAAG SERS substrate supporting highly reflective metal liquid-like films (MeLLFs) with polyacrylamide hydrogels (PAAG) has high-density "hot spots" to provide excellent SERS activity. The MeLLFs@PAAG formed by AgNPs only has less than 15% SERS activity loss when stored in the air for more than three weeks. By using rhodamine 6G (R6G) as a model analyte, the AgNPs based MeLLFs@PAAG SERS substrate exhibits an enhancement factor (EF) as high as 8.0 × 106, a limit of detection (LOD) of 76.8 pM (S/N = 3). Also, the formed PAAG provided a 3D molecular network to orderly secure the assembled nanoparticles (NPs), which not only improves the stability of NPs but also shields the Raman signal of proteins as high as 45 g/L allowing the direct determination of the binding rate of human serum albumin (HSA) and doxorubicin (DOX). A binding rate of about 70% was detected, which is consistent with previous reports. Thus, proposed the MeLLFs@PAAG SERS substrate can be used as a promising candidate for SERS measurement in complex biological samples.

Superior nitrogen-doped activated carbon materials for water cleaning and energy storing prepared from renewable leather wastes.

The fabrication of nitrogen-doped activated carbons (N-ACs) from leather solid wastes (LSW), a huge underutilized bioresource, by different activation methods was investigated. N-AC prepared by KOH activation (named KNAC) exhibited superior physical and chemical properties with much higher BET surface area (2247 m2 g-1) and more abundant hierarchical micropores than those activated by nano-CaCO3 (CNAC) or by direct carbonization (NNAC). KOH activation decreased the total nitrogen content in KNAC, but it increased the ratio of surface nitrogen species. KOH activation also significantly promoted the conversion of nitrogen species in the carbon material to pyridinic N. Potential applications of the prepared N-ACs were evaluated, and they were tested as adsorbents to remove phenols from water and as the anodes of lithium batteries. The high surface area, abundant micropores, and plentiful surface pyridinic N guaranteed KNAC a superior nitrogen-doped activated carbon that could serve as an excellent adsorbent to remove phenols (282 mg/g) from waste water as well as an outstanding electrode material with a high and stable charge/discharge capacity (533.54 mAh g-1 after 150th cycle). The strategy of LSW conversion to versatile N-ACs turns waste into treasure and could promote the sustainable development of our society.

Photocatalytic Conversion of Lignin into Chemicals and Fuels.

Lignin, an underutilized component of lignocellulosic biomass, is regarded as a rich reservoir for the production of aromatic chemicals and fuels. Despite extensive research in recent years, lignin's potential is far from being fully unlocked. Photocatalysis that uses sustainable solar energy to drive lignin conversion under mild conditions has been identified as a promising strategy and received growing research interest. This review aims to present a critical introduction to the photocatalytic conversion of lignin, including a summary of lignin conversion pathways and mechanisms, as well as the latest cutting-edge innovations on photocatalyst design and reactor construction. Moreover, the screening of solvents and regulation of other key factors that are involved in photocatalytic lignin conversion are also elucidated and future perspectives and challenges for photocatalytic conversion of lignin into valuable products are discussed.