Paired electrosynthesis is a promising technology with the potential to generate value-added products at both electrodes in a cost-effective manner. Herein, 3D vanadium nitride (VN) and Pd/VN hollow nanospheres are successfully fabricated and coupled to carry out simultaneous electrocatalytic oxidation (ECO) and electrocatalytic hydrogenation (ECH) of 5-hydroxymethylfurfural (HMF) into 2, 5-furandicarboxylic acid (FDCA) and 2,5-bishydroxymethyl-tetrahydrofuran (DHMTHF), respectively. VN shows excellent ECO performance with high HMF conversion (≥98%), FDCA selectivity (≥96%), and faradaic efficiency (≥84%) after a stability test, and Pd/VN achieves high ECH selectivity for DHMTHF at ≥88% and an HMF conversion of ≥90%, with a faradaic efficiency of ≥86%. VN and Pd/VN incorporated into a membrane electrode assembly in a paired electrolysis system shows potential for large-scale biomass conversion and upgrading. Theoretical calculations reveal that the higher performance of VN for the production of ECO can be attributed to its lower d-band center level relative to the Fermi level compared to that of V 2 O 5 , which favors HMF chemisorption and activation. This study paves the way for developing paired electrosynthesis technologies with the potential for biomass utilization and energy conversion.

Microporous covalent organic frameworks (COFs) hold great potential for small molecule separation but are yet challenging to design and synthesize. Here we report a framework interpenetration strategy to make microporous COFs for efficient separations of C8 alkyl-aromatic isomers. Two pairs of microporous three-dimensional (3D) salen- and Zn­(salen)-based COFs are prepared by Schiff-base condensation of ethanediamine with tetrahedral tetra­(salicylaldehyde)-silane or -methane derivatives in the presence or absence of metal ions. The four 3D COFs are isostructural and have a 7-fold interpenetrated diamondoid open framework with less than 8.0 Å wide tubular channels. They exhibit permanent porosity, high thermal stability, and good chemical resistance. The two COFs functionalized with uncoordinated salen groups can serve as stationary phases for high-performance liquid chromatography to provide baseline separation of xylene isomers and ethylbenzene with excellent column efficiency and precision, whereas the COFs with Zn­(salen) motifs cannot achieve high-resolution separation. The salen-COFs showed high affinity to the o-xylene, allowing fast and selective separation of the o-isomer from the other isomers within 7 min. This is the first report utilizing COFs to separate the practically important aromatic isomers. This work highlights new opportunities in designing microporous COFs and paves the way to expand the potential applications of COF materials.

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The electrocatalytical process is the most efficient way to produce ammonia (NH 3 ) under ambient conditions, but developing a highly efficient and low-cost metal-free electrocatalysts remains a major scientific challenge. Hence, single atom and double boron (B) atoms doped 2D graphene-like carbon nitride (C 2 N-h2D) electrocatalysts have been designed (B@C 2 N and B 2 @C 2 N), and the efficiency of N 2 reduction reaction (NRR) is examined by density functional theory calculation. The results show that the single and double B atoms can both be strongly embedded in natural nanoporous C 2 N with superior catalytic activity for N 2 activation. The reaction mechanisms of NRR on the B@C 2 N and B 2 @C 2 N are both following an enzymatic pathway, and B 2 @C 2 N is a more efficient electrocatalyst with extremely low overpotential of 0.19 eV comparing to B@C 2 N (0.29 eV). In the low energy region, the hydrogenation of N 2 is thermodynamically more favorable than the hydrogen production, thereby improving the selectivity for NRR. Based on these results, a new double-atom strategy may help guiding the experimental synthesis of highly efficient NRR electrocatalysts.

Stabilizing single-atom metal catalysts with carbon materials and utilizing their synergistic effect remains challenging due to weak interactions between carbon-based supports and metals. Density functional theory (DFT) calculations indicate that a single Ru atom was supported on a wide range of natural nanoporous carbon materials, including C 2 N, triazine-C 3 N 4 (T-C 3 N 4 ), and γ -graphene. These carbon materials belong to a new generation of highly efficient electrocatalysts for the N 2 reduction reaction (NRR) and are named Ru 1 @C 2 N, Ru 1 @T-C 3 N 4 , and Ru 1 @γ -graphyne, respectively. Ab initio molecular dynamic (AIMD) simulations show that a single Ru atom can be stably anchored in the nanopores of these carbon materials with strong cohesive energy. Compared with parallel adsorption configuration, the vertical adsorption configuration of N 2 exhibits higher adsorption energy. The calculated Gibbs free energy reveals N 2 reduction on the three catalysts via associative mechanisms. Despite the similar limiting potentials (−0.96, −0.94, and −0.98 V on Ru 1 @C 2 N, Ru 1 @T-C 3 N 4 , and Ru 1 @γ -graphynes, respectively), the limiting step differs, indicating the significant effects of carbon material substrates on electrochemical NRR. However, the competitive and efficient hydrogen evolution reaction (HER) changes the potential determining step and increases the overpotential for the electrochemical nitrogen reduction (NRR). This study provides insights for experimental synthesis of electrocatalysts for N 2 reduction.