Bao-Hua Xu

The in-situ reconstruction of catalysts has increasingly garnered research interest due to its pivotal role in modulating selectivity and improving activity. The surface reconstruction of group IVA element-based compounds under reaction conditions has been rarely investigated, despite wide application as active sites or carriers in catalyst fabrication. In this work, the heavy-period element in group IVA exhibits high activity in the electrocatalytic reduction of formaldehyde (HCHO) with H₂O, which is attributed to the accelerated proton-coupled electron transfer by strong HCHO adsorption. Remarkably, the proper reconstruction of metallic Si to Si-OH during the electrolysis accounts for the active surface, enabling a highly selective formation of ethylene glycol (EG). Competitive long-term stability (1500 h) is demonstrated at –200 mA cm^–2 with a low-resistance Si sheet as the cathode, which highlights the industrialization prospects of this alternative route for EG production.

The alkyl chain length in PlL-Ag hybrids influences the intrinsic activities for *COOH and *OCHO intermediates. Creating a *H-rich microenvironment with optimized CO ₂ mass transfer achieves a FE _HCOOH /FE _CO ratio of 0.87 under acidic conditions.

In this study, atomically dispersed metal catalysts of Salen-PIL(M) (M = Zn and Cu) for electrochemical CO₂-to-C₁ conversion were fabricated by polymerization of a vinyl-decorated ionic liquid (IL) monomer bearing a Salen-M moiety with para-diethylbenzene. The characterization results indicated that the Salen-Zn/Cu complex was atomically dispersed in the PIL skeleton. They differed significantly in the electron transfer speed to CO₂, CO affinity, and H₂O activation, which influenced both the activity and selectivity toward CO or CH₄. Besides, the formation of CO₂^•-* and H₂O activation were related to the tolerance of the pH range. Meanwhile, the adjustment of the interfacial H₂O content by introducing a hydrophobic IL benefited the competitive CO₂RR versus HER on Salen-PIL(Zn/Cu) catalysts. As a result, Salen-PIL(Zn) provided a CO faradaic efficiency (FE_CO) of 90.1% with a partial current density (j_CO) of 90.1 mA cm^-2 at -0.85 V, while a FE_CH4 of 54.5% with j_CH4 of 272.5 mA cm^-2 at -1.60 V was obtained on Salen-PIL(Cu).

In this study, copper-catalyzed reductive hydroamination of alkenes and 1,3-dienes with nitroarenes was developed. Such umpolung hydroamination of unsaturated C═C double bonds exhibited Markovnikov selectivity, and the hydroamination of 1,3-dienes preferred 1,2-addition. Mechanistic studies suggested the system proceeds through a radical pathway with the concomitant activation of both substrates to nucleophilic alkyl radical species and electrophilic nitro-based intermediates, respectively. The attack of alkyl radical species on the N atom of nitro-based intermediates yielded the desired amines. However, this C-N cross-coupling strongly competed with the self-reduction of each species under such a system.