Taizhou University

Investigating structural and hydroxyl group effects in electrooxidation of alcohols to value-added products by solid-acid electrocatalysts is essential for upgrading biomass alcohols. Herein, we report efficient electrocatalytic oxidations of saturated alcohols (C1-C6) to selectively form formate using NiCo hydroxide (NiCo–OH) derived NiCo2O4 solid-acid electrocatalysts with balanced Lewis acid (LASs) and Brønsted acid sites (BASs). Thermal treatment transforms BASs-rich (89.6%) NiCo–OH into NiCo2O4 with nearly equal distribution of LASs (53.1%) and BASs (46.9%) which synergistically promote adsorption and activation of OH− and alcohol molecules for enhanced oxidation activity. In contrast, BASs-enriched NiCo–OH facilitates formation of higher valence metal sites, beneficial for water oxidation. The combined experimental studies and theoretical calculation imply the oxidation ability of C1-C6 alcohols increases as increased number of hydroxyl groups and decreased HOMO–LUMO gaps: methanol (C1) < ethylene glycol (C2) < glycerol (C3) < meso-erythritol (C4) < xylitol (C5) < sorbitol (C6), while the formate selectivity shows the opposite trend from 100 to 80%. This study unveils synergistic roles of LASs and BASs, as well as hydroxyl group effect in electro-upgrading of alcohols using solid-acid electrocatalysts.

Immune checkpoint inhibitors (ICIs) have emerged as a transformative approach in cancer treatment, yet their efficacy is often limited by low response. Cuproptosis is a novel form of regulated cell death with lipoylated protein aggregation and iron‑sulfur (FeS) cluster protein destabilization. Here, we fabricated a PD-L1 nanobody-engineered bacterial outer membrane vesicles (OMVs) delivering elesclomol (ES) micelles for enhanced immunotherapy in triple-negative breast cancer (TNBC). By decorating OMVs with PD-L1 nanobodies, we enhance the tumor-targeting delivery efficiency of cuproptosis nanoinducers and PD-L1 blockade capability. Simultaneously, the engineered OMVs delivering ES micelles exhibited enhanced cytotoxicity against breast cancer cells via inducing cuproptotic cell death. In mice bearing 4 T1 xenografts, OMV-PD-L1nb@ES demonstrated significant tumor growth suppression. Notably, our nanoparticles elicited a robust antitumor immune response with increased infiltration and activation of CD8⁺ T cells and Treg depletion. By integrating cuproptotic tumor death with immune checkpoint blockade, the dual-functional nanoplatform represents a promising strategy for potentiated immunotherapy.

Electrocatalytic urea synthesis from CO₂ and NO₃^- offers a sustainable alternative to conventional energy-intensive industrial processes. However, it remains hindered by sluggish CN coupling kinetics and mismatched CO₂/NO₃^- reduction rates. Herein, a carbon quantum dots (CQDs)/metal-organic framework (MOF) heterostructure (Cu-MOF-CQD) was constructed by integrating amino-rich CQDs into the porous Cu-BTC framework (BTC = 1,3,5-benzenetricarboxylic acid) via a one-step ultrasonic-static strategy. The integration of CQDs markedly enhances the electrical conductivity of Cu-MOF and modulates the interfacial electronic structure through interactions between CQDs surface groups and unsaturated Cu sites within Cu-MOF, thereby enriching high-valence Cu species and facilitating charge transfer. Operando spectroscopic characterizations combined with density functional theory calculations unveil that the interface effect of Cu-MOF-CQD provides a stronger driving force for *COOH to *CO conversion and accelerates the coupling of *CO and *NH₂ intermediates, thus promoting efficient CN bond formation. Benefiting from this synergistic interface, in a flow cell, Cu-MOF-CQD achieves a maximum urea Faradaic efficiency of 18.5 ± 0.7 % at -0.5 V vs. RHE and the corresponding urea yield rate of 260.2 ± 10.1 μg h^-1 mg_cat^-1, surpassing the performance of pristine Cu-MOF. This work establishes a generalizable strategy of zero-dimensional carbon/MOF heterostructures for boosting CN coupling performance, offering new design principles for next-generation electrocatalysts in sustainable CN coupling reactions.