Partially Nitrided Ni Nanoclusters Achieve Energy-Efficient Electrocatalytic CO2 Reduction to CO at Ultralow Overpotential.

Electrocatalytic CO2 reduction reaction (CO2 RR) offers a promising strategy to lower CO2 emission while producing value-added chemicals. A great challenge facing CO2 RR is how to improve energy efficiency by reducing overpotentials. Herein, partially nitrided Ni nanoclusters (NiNx ) immobilized on N-doped carbon nanotubes (NCNT) for CO2 RR are reported, which achieves the lowest onset overpotential of 16 mV for CO2 -to-CO and the highest cathode energy efficiency of 86.9% with CO Faraday efficiency >99.0% to date. Interestingly, NiNx /NCNT affords a CO generation rate of 43.0 mol g-1  h-1 at a low potential of -0.572 V (vs RHE). DFT calculations reveal that the NiNx nanoclusters favor *COOH formation with lower Gibbs free energy than isolated Ni single-atom, hence lowering CO2 RR overpotential. As NiNx /NCNT is applied to a membrane electrode assembly system coupled with oxygen evolution reaction, a cell voltage of only 2.13 V is required to reach 100 mA cm-2 , with total energy efficiency of 62.2%.

Carbazolic Conjugated Organic Polymers for Visible-Light-Driven CO2 Photoreduction with H2 O to CO with High Efficiency and Selectivity.

Visible-light-driven CO2 photoreduction with H2 O to value-added chemicals in high efficiency and selectivity is significant but challenging. Herein, a series of carbazolic conjugated organic polymers (CB-COPs) with electron donor-acceptor (D-A) structures were prepared, which showed high efficiency for visible-light-driven photocatalytic reduction of CO2 with H2 O in a solid-gas mode, affording CO as the exclusive carbonaceous product. Especially, CB-COP-mpd derived from 3,5-di(9H-carbazol-9-yl)pyridine exhibited the highest CO evolution rate up to 191.46 µmol g-1 h-1 with a selectivity of 100 %. Mechanism studies showed that carbazolyl is a promising electron donor candidate for constructing CB-COPs with D-A structures, capable of improving the catalytic efficiency and suppressing H2 generation. The acceptor building block with excessive electron withdrawing capability was favorable to H2 O adsorption, thus resulting in the generation of H2 . This work provides new insights for designing COPs photocatalysts for CO2 photocatalytic reduction.

Amide-bridged conjugated organic polymers: efficient metal-free catalysts for visible-light-driven CO2 reduction with H2O to CO.

The visible-light-driven photoreduction of CO2 to value-added chemicals over metal-free photocatalysts without sacrificial reagents is very interesting, but challenging. Herein, we present amide-bridged conjugated organic polymers (amide-COPs) prepared via self-condensation of amino nitriles in combination with hydrolysis, for the photoreduction of CO2 with H2O without any photosensitizers or sacrificial reagents under visible light irradiation. These catalysts can afford CO as the sole carbonaceous product without H2 generation. Especially, amide-DAMN derived from diaminomaleonitrile exhibited the highest activity for the photoreduction of CO2 to CO with a generation rate of 20.6 µmol g-1 h-1. Experiments and DFT calculations confirmed cyano/amide groups as active sites for CO2 reduction and second amine groups for H2O oxidation, and suggested that superior selectivity towards CO may be attributed to the adjacent redox sites. This work presents a new insight into designing photocatalysts for artificial photosynthesis.

Highly Compressible and Sensitive Pressure Sensor under Large Strain Based on 3D Porous Reduced Graphene Oxide Fiber Fabrics in Wide Compression Strains.

The development of highly sensitive wearable and foldable pressure sensors is one of the central topics in artificial intelligence, human motion monitoring, and health care monitors. However, current pressure sensors with high sensitivity and good durability in low, medium, and high applied strains are rather limited. Herein, a flexible pressure sensor based on hierarchical three-dimensional and porous reduced graphene oxide (rGO) fiber fabrics as the key sensing element is presented. The internal conductive structural network is formed by the rGO fibers which are mutually contacted by interfused or noninterfused fiber-to-fiber interfaces. Thanks to the unique structures, the sensor can show an excellent sensitivity from low to high applied strains (0.24-70.0%), a high gauge factor (1668.48) at an applied compression of 66.0%, a good durability in a wide range of frequencies, a low detection limit (1.17 Pa), and anultrafast response time (30 ms). The dominated mechanism is that under compression, the slide of the graphene fibers through the polydimethylsiloxane matrix reduces the connection points between the fibers, causing a surge in electrical resistance. In addition, because graphene fibers are porous and defective, the change in geometry of the fibers also causes a change in the electrical resistance of the composite under compression. Furthermore, the interfused fiber-to-fiber interfaces can strengthen the mechanical stability under 0.01-1.0 Hz loadings and high applied strains, and the wrinkles on the surface of the rGO fibers increased the sensitivity under tiny loadings. In addition, the noninterfused fiber-to-fiber interfaces can produce a highly sensitive contact resistance, leading to a higher sensitivity at low applied strains.

Rational Design of Layered SnS2 on Ultralight Graphene Fiber Fabrics as Binder-Free Anodes for Enhanced Practical Capacity of Sodium-Ion Batteries.

Generally, the practical capacity of an electrode should include the weight of non-active components such as current collector, polymer binder, and conductive additives, which were as high as 70 wt% in current reported works, seriously limiting the practical capacity. This work pioneered the usage of ultralight reduced graphene fiber (rGF) fabrics as conductive scaffolds, aiming to reduce the weight of non-active components and enhance the practical capacity. Ultrathin SnS2 nanosheets/rGF hybrids were prepared and used as binder-free electrodes of sodium-ion batteries (SIBs). The interfused graphene fibers endow the electrode a porous, continuous, and conductive network. The in situ phase transformation from SnO2 to SnS2 could preserve the strong interfacial interactions between SnS2 and graphene. Benefitting from these, the designed binder-free electrode delivers a high specific capacity of 500 mAh g-1 after 500 cycles at a current rate of 0.5 A g-1 with almost 100% Coulombic efficiency. Furthermore, the weight percentage of SnS2 in the whole electrode could reach up to 67.2 wt%, much higher than that of common electrode configurations using Cu foil, Al foil, or carbon cloth, significantly highlighting the ultralight characters and advantages of the rGF fabrics for using as binder-free electrodes of SIBs.

Ionic liquid/H2O-mediated synthesis of mesoporous organic polymers and their application in methylation of amines.

Mesoporous Tröger's base-functionalized polymers (Meso-TBPs) were prepared using a sulfonic acid group functionalized ionic liquid/H2O system, with surface areas up to 431 m2 g-1 and pore sizes of 3-15 nm. Ir(ii) coordinated Meso-TBPs exhibited extraordinary catalytic performance in the N-methylation of amines using methanol.

N-Doped porous carbon nanotubes: synthesis and application in catalysis.

Uniform N-doped carbon nanotubes were obtained for the first time via a morphology-preserving thermal transformation of organic polymer nanotubes without any additional templates. These carbon nanotubes acted as a superior metal-free carbon catalyst for C-H arylation of benzene, reductive hydrogen atom transfer and oxidation reactions.

Hierarchically Mesoporous o-Hydroxyazobenzene Polymers: Synthesis and Their Applications in CO2 Capture and Conversion.

The synthesis of hierarchically mesoporous polymers with multiple functionalities is challenging. Herein we reported a template-free strategy for synthesis of phenolic azo-polymers with hierarchical porous structures based on diazo-coupling reaction in aqueous solution under mild conditions. The resultant polymers have surface areas up to 593 m(2) g(-1) with the mesopore ratio of >80 %, and a good ability to complex with metal ions, such as Cu(2+) , Zn(2+) ,Ni(2+) , achieving a metal loading up to 26.24 wt %. Moreover, the polymers complexed with Zn showed excellent performance for catalyzing the reaction of CO2 with epoxide, affording a TOF of 2570 h(-1) in the presence of tetrabutyl ammonium bromide (7.2 mol %). The polymer complexed with Cu could catalyze the oxidation of alcohol with high efficiency.

Azo-functionalized microporous organic polymers: synthesis and applications in CO2 capture and conversion.

Azo-functionalized MOPs (Azo-MOPs) were synthesized via oxidative polymerization of aromatic amines catalyzed by t-BuOCl/NaI (25 °C, 1 h, yield: >95%), which displayed an excellent coordinating ability with a Ru complex. The resulting Ru-coordinated Azo-MOPs displayed high CO2 capacity and high performances for catalyzing the methylation of amines with CO2 under low pressure (0.5 MPa).

Synthesis of metalloporphyrin-based conjugated microporous polymer spheres directed by bipyridine-type ligands.

Zinc porphyrin (TP-Zn)-based conjugated microporous polymer (Zn-CMP) spheres were obtained via Sonagashira-Hagihara cross coupling reactions between 5,10,15,20-tetrakis(4-ethynylphenyl)porphyrin-Zn(II) and brominated monomers directed by bidentate bipyridine (BP)-type ligands for the first time, and the sphere diameters could be adjusted from 320 to 740 nm. The coordination between BP and TP-Zn was proved to be the key to forming spheres.

A Tröger's base-derived microporous organic polymer: design and applications in CO2/H2 capture and hydrogenation of CO2 to formic acid.

A Tröger's base-derived microporous organic polymer (TB-MOP) was designed, which could adsorb CO2 and coordinate with a Ru(III) complex. The resultant TB-MOP-Ru showed good CO2 and H2 adsorbing performances, and high efficiency for catalysing hydrogenation of CO2 to HCOOH with a turnover number up to 2254 at 40 °C.

Fluorinated microporous organic polymers: design and applications in CO2 adsorption and conversion.

Fluorinated microporous organic polymers (F-MOPs) were designed, showing twice higher CO2 adsorption capacity than corresponding non-fluorous MOPs. The incorporation of phenanthroline moieties into F-MOPs afforded them the ability to coordinate with Ag(I), and the resultant F-MOP-Ag(I) displayed high efficiency for the reaction of CO2 with propargyl alcohols to form α-alkylidene cyclic carbonates at 25 °C.