ABSTRACT Direct photocatalytic upgrading of olefins into long‐chain oxygenates using water as the sole oxygen and hydrogen source is highly attractive, yet remains challenging due to the difficulty of integrating intermolecular C─C coupling with selective hydroxylation. Herein, we report a photocatalytic pathway for the direct synthesis of n ‐butanol from ethylene and water over an in situ‐constructed Pt@Cu core–shell cocatalyst supported on TiO 2 . Under illumination, water is dissociated to generate surface *H and *OH species, which are synchronously incorporated into two activated ethylene molecules, while the remaining carbon centers undergo intermolecular C─C coupling to construct the C 4 backbone, enabling one‐step formation of n ‐butanol. The Pt core promotes directional electron extraction from TiO 2 and continuously enriches the surrounding Cu shell with electrons, thereby facilitating both ethylene activation and water dissociation. Meanwhile, dissolved Cu 2+ dynamically regulates the surface Cu redox state and preserves a Cu(I)‐rich active surface during photocatalysis. As a result, the Pt@Cu core–shell catalyst in Cu 2+ solution achieves a C 4 oxygenate production rate of 749.9 µmol g −1 h −1 with selectivity of 63.3%. This work establishes a photocatalytic strategy integrating C─C coupling and hydroxylation for solar‐driven synthesis of long‐chain oxygenates from olefins and water.
ABSTRACT The practical application of metal sulfides in anion‐exchange membrane water electrolysis (AEMWE) is fundamentally hindered by the uncontrolled deep reconstruction under anodic conditions, which leads to rapid catalyst deactivation. Herein, with cobalt sulfide (Co 9 S 8 ) as a model, we introduce terbium (Tb) sites to frustrate deep reconstruction and relieve catalyst deactivation toward the oxygen evolution reaction (OER). The Tb‐Co 9 S 8 exhibits a low overpotential of 239 and 308 mV to reach 10 and 100 mA cm −2 , respectively toward OER. As an AEMWE anode, the Tb‐Co 9 S 8 achieves 1.0 A cm −2 at only 1.80 V and sustains continuous operation for 4200 h with a degradation rate of only 0.018 mV h −1 . The enhanced OER activity of Tb‐Co 9 S 8 originates from Tb incorporation, which inhibits deep bulk S‐O exchange and induces breathing‐like Co‐O coordination dynamics on the CoOOH active surface to curb over‐reconstruction and alleviate catalyst deactivation. Furthermore, asymmetric Tb atomic sites increase occupancy of spin‐state Co 3+ and optimize the local hydrogen‐bond network, which enhances lattice‐oxygen activation and renders *OH backfilling more spontaneous, thereby mitigating the activity‐stability trade‐off in the lattice oxygen mechanism. This work establishes a new rare‐earth‐mediated strategy to frustrate deep reconstruction and stabilize a real active surface for efficient and stable hydrogen production.
ABSTRACT Metal‐free purely organic phosphors (POPs) are attractive triplet emitters, but their room‐temperature phosphorescence (RTP) is often slow at milliseconds or longer because the radiative T 1 →S 0 transition is spin‐forbidden. Here, we introduce directional carbonyl orientation (DCO) as a packing‐aware conformational descriptor for understanding and designing fast metal‐free RTP. In brominated terephthalate derivatives, co‐directional carbonyl torsions are associated with fast RTP, whereas counter‐directional torsions are associated with slower RTP. Using two polymorphs of dimethyl dibromoterephthalate (MeBrTPA), we show that the co‐directional Form I emits blue RTP with Φ phos = 24%, τ phos = 15 µs, and an estimated k r = 1.6 × 10 4 s −1 , while the counter‐directional Form II is slower despite its higher quantum yield. State‐resolved TD‐DFT/SOC calculations further reveal that the difference cannot be described by direct S 0 –T 1 coupling alone, but instead reflects distinct state‐specific combinations of T 1 –S n SOC and S n –S 0 transition strength. Finally, translating the DCO‐favored geometry from crystal packing into molecular design, conformational locking in CyclicBrTPA produces fast blue RTP in amorphous PMMA. Together, these results establish DCO as a practical molecular design strategy for organizing favorable spin‐coupling geometries beyond a single crystal‐packing environment, while highlighting the continued importance of a sufficiently rigid environment for room‐temperature emission.
ABSTRACT Controlling the crystallographic facet orientation of in situ deposited products in conversion‐type batteries remains a fundamental challenge, as conventional synthesis‐based strategies cannot be applied to phases that nucleate and grow electrochemically during cell operation. Here, taking rechargeable Li||Cl 2 batteries as a model system, we elucidate the complete AlCl 4 − ‐mediated catalytic cycle governing the LiCl‐to‐Cl 2 charging conversion and identify the intrinsic covalent rigidity of the Al─Cl bond as the rate‐determining factor. On this basis, we propose an electronic polarization induced coordination (EPIC) strategy in which an in situ‐assembled [AlCl 2 (BZA) 2 ] + coordination cation (BZA = benzamide) activates directional N─H···Cl hydrogen bonds that selectively weaken the Al─Cl bond and lower the catalytic energy barrier. This molecular‐level intervention simultaneously redirects LiCl crystal growth from passivating {100} cubes toward dispersed {111}‐faceted nanocrystals through adsorption‐induced surface‐energy inversion, and operando x‐ray diffraction identifies these nanocrystals as the preferentially cycled, highly reversible phase, establishing a complete causal chain from coordination chemistry through catalytic kinetics to crystal facet engineering via a single design element. Li||Cl 2 cells employing the EPIC electrolyte sustain over 2500 stable cycles at −40°C under 1 A g −1 , tolerate current densities up to 30 A g −1 , and deliver 6.06 Ah in a cylindrical cell (ER26500) at 25°C.
ABSTRACT Electrocatalytic conversion of water‐soluble organics in aqueous media offers a sustainable route to high‐value chemicals, yet sluggish mass transport remains a critical bottleneck at industrially relevant current densities. Here, dimethyl sulfoxide (DMSO) is employed as the modifier to enhance mass transport by reconstructing hydrogen‐bond (H‐bond) networks. In the bulk electrolyte, DMSO inserts into the dense hydrogen bonds to expand the free‐volume distribution, releasing reactants from the solvation shell and accelerating their diffusion. Simultaneously, interfacial interactions between DMSO, reactants, and cations enrich local reactant concentrations, cooperatively facilitating the reaction kinetics. This dual‐enhancement mechanism achieves ∼60% Faradaic efficiency (FE) in electrocatalytic dehalogenative hydrogenolysis at 300 mA cm −2 . Our strategy demonstrates broad utility across the dehalogenative hydrogenation of other halogenated substrates and the hydrogenation of nitriles/nitro compounds, delivering >10% FE improvements. By coupling bulk diffusion acceleration with interfacial reactant enrichment, this work offers a promising strategy to overcome mass transport limitations in aqueous electrosynthesis.
