Dalian National Laboratory for Clean Energy

ABSTRACT Water‐induced structural dynamics of zeolite framework have been extensively explored in binary model systems comprising only water and zeolites. However, under practical zeolite catalytic systems, water coexists with organic guest molecules within the confined microporous environment, giving rise to dynamical and multicomponent host–guest interactions. Combining in situ spectroscopic characterization with theoretical calculations, this study unveils, at the molecular level, the dynamic ternary interplay among zeolite, confined aromatics, and water during SAPO‐34‐catalyzed methanol‐to‐olefins (MTO) reaction. The confined aromatics generated in situ spatially and electronically modify the zeolite framework, forming a molecular shield that protects the zeolite framework from hydrolytic attack. More importantly, water acts as a molecular scissor, continuously trimming the alkyl side‐chains of confined aromatics, thereby retarding their polycyclic growth while promoting the efficient and sustained formation of light olefins. Across a series of eight‐membered‐ring (8‐MR) zeolites (SAPO‐34, SAPO‐18, and SSZ‐13), co‐feeding water results in an orders‐of‐magnitude enhancement of catalyst lifetime while maintaining stable olefin production. The dynamic cooperative interplay among zeolite, confined aromatics, and water governs the framework stability and catalytic longevity during MTO conversion. This mechanistic insight extends the conceptual boundaries of zeolite host–guest chemistry and opens new avenues for harnessing the beneficial role of water in zeolite catalysis.

Ethylene methoxycarbonylation (EMC) reaction, a key carbonylation process for methyl propionate production, typically relies on acid promoters and phosphine ligands in conventional homogeneous systems. Although heterogeneous Ru cluster catalysts can eliminate these additives, they still suffer from a low noble-metal utilization efficiency. Herein, we report an atomically dispersed dual-site catalyst Ru1Co1/MIL-101-EDTA for the EMC reaction, where the Ru1 and Co1 atoms are anchored on the EDTA-modified MIL-101(Cr) framework. The catalyst achieved a turnover frequency (TOF) of 125.6 h–1, which was 4.8-fold higher than that of the monometallic Ru1/MIL-101-EDTA counterpart, while maintaining 99.9% selectivity for methyl propionate without any decay over 5 recycles, being the most active Ru-based heterogeneous EMC catalyst reported to date. Experimental and theoretical studies revealed that the Cr(III) Lewis acid sites in the MIL-101(Cr) framework play a vital role in methanol dissociation, thus avoiding the addition of acid additives. The Co1 sites act as the primary *H adsorption centers and optimize the *CO adsorption path, thereby lowering the CO insertion barrier. Meanwhile, the electronic interaction between the Ru1 and Co1 species lowers the energy barrier for the rate-determining nucleophilic of the methoxyl group.

Anode-free solid-state lithium metal batteries offer high energy density and enhanced safety, but their development is hindered by unstable solid electrolyte interphase formation and uncontrolled lithium deposition, which cause rapid capacity decay. To address these challenges, we introduced a smart non-sacrificial interphase (SNI) using 5-nitro-2-mercaptobenzimidazole (N-MBI) additive. N-MBI spontaneously forms an ultrathin self-assembled layer on copper current collectors before lithium deposition, creating a protective interface that isolates lithium metal from the electrolyte and suppresses parasitic reactions. During initial lithiation, the adsorbed N-MBI undergoes in-situ lithiation to form 5-amino-2-mercaptobenzimidazole lithium (Li-NH2-MBI), which maintains strong interfacial adhesion and preferential affinity with lithium metal. This Li-NH2-MBI SNI guides uniform lithium nucleation and growth beneath the protective interface, preventing dendrite formation. As a result, electrolyte decomposition is minimized, and lithium deposition and dissolution are highly reversible. This approach significantly improves performance: Li|Cu half-cells achieve an average Coulombic efficiency of 99.3%, and Cu||LiFePO4 pouch cells retain 52.4% capacity at 0.2 C after 100 cycles, a 19.6% improvement over the widely adopted LiNO3 sacrificial additive. At 0.5C, the N-MBI additive increases capacity retention after 100 cycles to 55.4%. The work validates an effective molecular-level strategy for stabilizing lithium metal anodes in anode-free configurations through SNI design.

ABSTRACT The spontaneous polarization in ferroelectric perovskites offers a promising route toward self‐powered X‐ray detection, yet the microscopic link between ferroelectric phase transition and detector‐relevant carrier dynamics remains largely unexplored. Here, using 1D [3‐(aminomethyl)piperidinium]BiI 5 single crystals (3AMP SCs) as a model system, we uncover how a specific first‐order ferroelectric–paraelectric transition mechanism directly governs polarization‐driven carrier transport and photovoltaic behavior. Structural analyses reveal that room‐temperature ferroelectricity originates from the non‐centrosymmetric ordering of 3AMP 2 + cations and strong organic–inorganic interfacial coupling, while the transition at 364 K is driven by highly anharmonic hydrogen‐bond dynamics and stabilized by the rigidity of the Bi–I framework. This cooperative mechanism generates a robust polarization field along the c‐axis, which reduces exciton binding energy, suppresses trap‐assisted recombination, and enables efficient carrier separation through the bulk and anomalous photovoltaic effects. As a direct consequence of this phase‐transition‐controlled transport behavior, the 3AMP SC‐based detector achieves record‐performance self‐powered X‐ray detection, with a sensitivity of 566.79 µC Gy air −1 cm −2 , an ultra‐low detection limit of 5.24 nGy air s −1 , and excellent long‐term stability. This work establishes a clear structure–phase transition–polarization–transport–performance relationship in Bi‐based halide perovskites, providing a new framework for designing ferroelectric materials for self‐powered optoelectronic devices.

The strong interactions arising from stable coordination structures in single-atom catalysts (SACs) may confer certain antideactivation properties in the presence of poisons like CO and H2S. However, such strong bonding often limits reactivity in ongoing catalytic reactions. This study introduces a Ni-NC SAC where single-atom active sites, stabilized by pyridine nuclei in a classical N5 square-pyramidal coordination geometry, create a stable, efficient, and selective catalyst for H2S-to-S8 oxidation. Unlike the typical Ni–N4 square-planar geometry, the addition of a fifth axial pyridinic N donor enhances the electron density of the monatomic Ni site, reducing the activation energy of intermediate HS* species from 2.62 to 1.12 eV. Weak interactions between the S8 product and the monatomic Ni active center facilitate product desorption, preserving active site integrity. Consequently, the Ni-NC catalyst demonstrates high H2S-to-S8 performance (354 gS kgcat–1 h–1), long-term stability (>100 h), and resistance to common impurities like CO, CO2, and H2O from biomass or blast furnace gas under high GHSV (30 L g–1 h–1) and high H2S concentration (10000 ppm). This work offers insights into designing robust SACs for poisoning reagent removal catalysis and suggests potential applications in the desulfurization industry.

Defects at the buried interface represent a critical challenge that impedes further improvements in both the performance and scalable manufacturing of perovskite solar cells (PSCs). Defect formation, lattice mismatch, and energy-level misalignment at this interface aggravate nonradiative recombination and accelerate photothermal degradation, thereby limiting both efficiency and operational stability. Here, we employ interface engineering using multifunctional molecules to suppress defect formation. To minimize redundant material screening, we combine theoretical calculations with experimental validation to identify 4-aminobutylphosphonic acid (4-ABPA) for modifying the interface between the perovskite layer and the electrode. Both simulation and experimental results demonstrate 4-ABPA as a multifunctional molecular bridge that simultaneously anchors to the charge transport layer and interacts with the perovskite lattice. And its role in dynamically regulating perovskite crystallization and enhancing interfacial performance is uncovered. The dual-site chemical binding regulates crystallization, alleviates residual stress, suppresses interfacial defects, and optimizes energy-level alignment at the buried interface. As a result, voltage loss is reduced to 31mV, enabling power conversion efficiencies of 25.56% in n-i-p and 26.45% in p-i-n architectures with negligible hysteresis. The modified devices also exhibit outstanding durability, retaining 83.91% of their initial performance under 1440 h of continuous operation and 91.59% after 2600 h of ambient storage. Our work establishes a systematic and universal buried-interface engineering strategy to further enhance efficiency and stability, thereby advancing the mass production of perovskite devices.

ABSTRACT The low‐temperature direct conversion of ethane is more appealing for the utilization of shale gas. Dual‐atom catalysts have attracted considerable attention due to their unique cooperative effects. Herein, we report a porous organic polymer‐supported Rh 1 –Cu 1 dual‐site catalyst (Rh 1 –Cu 1 @POPs‐PPh 3 ) for the selective oxidation of ethane to ethanol, acetaldehyde, and acetic acid with auto‐selective oxygen mechanism. The optimized Rh 1 –Cu 1 centers deliver a productivity of ca. 250 mol mol Rh −1 h −1 based on Rh with 65% acetaldehyde selectivity at 423 K, representing a four‐fold improvement over the single‐Rh‐site catalyst. Through isotopic labeling and in situ characterizations, we uncover an auto‐selective oxygen source mechanism in which dehydrogenated species of ethane with different grades possess self‐selectivity for the combined oxygen source. Oxygen species derived from O 2 activate ethane and subsequently couple with the ethyl fragment to produce ethanol. While OH radicals from H 2 O dissociation react with ethyl intermediates from ethane dehydrogenation to yield acetaldehyde. Concurrently, oxygen species recombine with reactive hydrogen species to regenerate new H 2 O, completing the catalytic oxidation cycle. The density functional theory (DFT) calculations reveal that the Rh–Cl–Cu configuration lowers the lowest unoccupied molecular orbital (LUMO) energy of Rh 1 , thereby strengthening adsorbate‐metal interactions, weakening the C─H bond, and facilitating its activation.