ABSTRACT Electrochemical C─N coupling of CO 2 with nitrogen species offers a sustainable route to urea and related chemicals but is constrained under steady‐state electrolysis by mismatched reaction kinetics. Here, pulsed oxidative–reductive electrolysis temporally coordinates CO 2 reduction and NH 3 oxidation, regulating the generation and coexistence of carbon‐ and nitrogen‐derived intermediates. Co/CuNC, containing atomically dispersed Co and Cu sites within a nitrogen‐doped carbon (NC), achieves a total C─N faradaic efficiency of 42 ± 4%, dominated by urea (20 ± 2%) and ethyl urea (16 ± 2%), with respective yield rates (YR) of 295 ± 25 and 50 ± 5 mmol h −1 g cat −1 . In situ synchrotron x‐ray absorption spectroscopy (XAS) reveals potential‐dependent changes in Cu and Co oxidation states and coordination environments, while in situ infrared spectroscopy identifies pulse‐regulated *CO and *NH x intermediates and suggests concurrent electrochemical and Wöhler‐type pathways. Density functional theory calculations reveal complementary site functions: Cu favors *NH 2 formation, whereas Co more strongly stabilizes *NH x and *CO intermediates, with *CO also accessible at Cu sites. These findings establish temporal coordination of reactant activation, intermediate populations, and active‐site states as a mode‐enabled strategy for accessing higher‐order C─N products.
ABSTRACT Chiral‐lattice degrees of freedom can offer novel chirality‐selective functionalities for thermotronic applications. Chiral phonons, which carry both heat and angular momentum, can arise from broken chiral degeneracy in phonon bands or from angular momentum transfer from photons or spins. Here, we demonstrate a nanoscale chirality‐selective phonon transport based on a simple heterostructure of ferromagnetic [Co/Pt] multilayers and insulating chiral α‐SiO 2 . Using magneto‐optic thermometry, we show that the effective thermal conductivity of α‐SiO 2 depends systematically on both the magnetization direction of [Co/Pt] and the structural handedness of α‐SiO 2 . This behavior is supported by first‐principles‐based molecular dynamics simulations, which reveal chirality‐dependent phonon transport across the ferromagnet/chiral‐material interface. The magnetization‐dependent thermal on/off ratio reaches 1.07 at room temperature and increases to approximately 1.2 at 50 K, reflecting reduced Umklapp phonon–phonon scattering. These results establish a ferromagnet/chiral‐material platform for controlling nanoscale heat flow through chiral phonons.
ABSTRACT Deep mineralization and matrix tolerance are difficult to reconcile in advanced oxidation processes because radical and nonradical pathways are often coupled in a composition‐defined paradigm. Although multimetal materials can catalyze both pathways, the parallel reactions typically occur at different active sites, and their relative contributions are often governed by catalyst composition and active‐site distribution, making deliberate regulation of pathway competition difficult. Here, we propose a multimetal catalyst with an electronically asymmetric Fe─O─Co interface to enable pathway divergence within a Co‐centered catalytic environment. Fe introduction into CoNi layered hydroxides leads to electron density redistribution at neighboring Co sites and shifts PMS activation from a high‐valent Co IV ═O‐biased route toward a sulfate‐radical‐enriched regime while retaining complementary nonradical oxidation. The optimized catalyst achieved 1.43‐fold greater TOC removal and a 1.47‐fold higher PMS utilization efficiency (PUE) for norfloxacin (NOR) degradation than the Fe‐free control, with robust decontamination performance against common background matrix interference and sustained activity over 96 h of high‐flux continuous‐flow operation. This work establishes interfacial Fe regulation as a pathway‐engineering strategy for steering oxidant‐activation selectivity through heterometal‐induced electronic asymmetry, providing a route to reconcile mineralization depth with matrix tolerance in Fenton‐like water treatment.
ABSTRACT Low infrared emissivity materials (i.e., metallic materials) are of significance for thermal radiation regulation. However, the easy‐corrosion susceptibility and poor chemical stability are common bottleneck issues that affect their applications. We report a versatile electronic structure modulation strategy for low infrared (IR) emissivity graphene by engineering the surface chemistry of precursor graphene oxide and the followed reduction/doping process. The fabrication protocols minimize the irreparable disruption of the intrinsic graphitic structure and enable controllable assembly of nanosheets by suppressing formation of carboxyl groups. More significantly, the convenient reduction and halogen doping effects synergistically minimize electron scattering and enhance interfacial charge transport. The low‐defective graphitic structure and the ordered multiscale architecture, as well as halogen doping effect, afford exceptional carrier mobility (∼27.1 cm 2 V −1 s −1 ), carrier density (5.73 × 10 20 cm −3 ), and electrical conductivity comparable to highly oriented pyrolytic graphite. Surprisingly, the anomalous metallic response gives the lowest IR emissivity (0.15, 8–14 µm) for carbon materials, comparable to MXene and traditional metallic materials. The large‐scale processability and outstanding long‐term stability under chemical conditions offer new insights for the potential infrared applications of graphene materials.
