The interface structures between dissimilar layers in perovskite solar cells (PSCs) are prone to the concurrent occurrence of lateral (in-plane) chemical aggregation and vertical (out-of-plane) mechanical delamination. This issue severely affects long-term optoelectronic processes in PSCs, and it has not been addressed holistically. Herein, we introduce an ultrathin interfacial layer of 1,3,6,8-pyrenetetrasulfonic tetrasodium salt (PTS) to stabilize the perovskite/C60 interface at the molecular level. The sulfonate groups in PTS molecules anchor to the perovskite interface, while the parallelly aligned pyrene cores establish robust π-π interactions with C60 molecules. The reconstructed interface enhances the interfacial adhesion and restricts the mobility of C60 molecules, enabling a bidirectional chemo-mechanical interface stabilization (BCIS) mechanism at the perovskite/C60 interface. The resultant PSCs deliver power conversion efficiencies (PCEs) of up to 26.53%, showing 96% PCE retention after 1,000 h maximum-power-point tracking (ISOS-L-1l), and 91% PCE retention after 300 thermal cycles (-40 to 85 °C, IEC61215 MQT11). The scalability of PTS treatment is demonstrated by the 818 cm2 (aperture area) perovskite solar modules (PSMs) with PCEs over 20% using industrial-compatible manufacturing processes under 55% relative humidity (RH). This work underscores bidirectional interface engineering as a critical strategy for advancing commercially viable perovskite photovoltaics.

Halide-substituted argyrodite materials have attracted increasing attention for energy applications since compositional tuning provides an effective strategy to modulate their structure and transport characteristics. While Li+-based halide argyrodites have been extensively studied, a unified composition-resolved understanding of Cu+-based halide argyrodites that integrates phase evolution, local structure, lattice dynamics, and electronic and ionic transport remain limited. In this work, we investigate Cu6PS5X (X = Cl, Br, I, Cl0.5Br0.5, Cl0.5I0.5, and Br0.5I0.5) within a combined experimental and computational framework. All compositions adopt an average cubic F4̅3m structure at room temperature, while local structural analysis reveals deviations from cubic symmetry consistent with a monoclinic Cc model involving PS43- tetrahedral tilting. 31P MAS NMR spectroscopy corroborates this local symmetry breaking through multiple distinct phosphorus environments arising from relative tetrahedral orientation rather than S2-/X- site disorder. Halide substitution modifies the Cu+ conductivity through changes in the activation energy and the Arrhenius pre-exponential factor, following the Meyer-Neldel behavior, with additional contributions from variations in jump distances and migration pathways. Direction-projected phonon density of states analysis identifies low-frequency Cu+ vibrational components along the crystallographic migration pathways. Analysis of the Meyer-Neldel slope further suggests phonon assisted ion hopping involving multiphonon excitation of low-frequency Cu+ vibrational modes. Together, these findings offer insight into structure-property relationships in Cu6PS5X and suggest that, alongside the migration energy landscape, the vibrational energy scale, thermal population, and directionality of mobile ion modes should be considered when interpreting ion transport, thereby providing a vibrational perspective for the design of solid-state ion conductors.

Scaling proton exchange membrane fuel cells (PEMFCs) is constrained by high cathodic overpotential and platinum usage for the oxygen reduction reaction, challenges exacerbated by catalyst poisoning from perfluorosulfonic acid (PFSA) ionomers. Though compositing PFSA with additives can mitigate this poisoning, progress has remained largely empirical due to the lack of quantitative assessment tools. Here, we introduce an electrochemical probe leveraging ionomer-coated single-crystal Pt(111) to quantify the coverage and strength of PFSA adsorption, elucidating how cationic additives suppress Pt poisoning. We identify an inverse correlation between cation hydration energy and PFSA adsorption, guiding the rational design of a poorly hydrated tetramethylammonium-anchored covalent organic framework (TMA+-COFs) as an ionomer additive. Electrochemical and spectroscopic analyses reveal that the composite TMA+-COFs/PFSA layer significantly inhibits sulfonate adsorption and poisoning onto Pt(111) through robust electrostatic interactions, which translates to a 1.7- and 4-fold activity enhancement for industrial Pt/C in rotating-disk and gas-diffusion electrodes, respectively. We also demonstrated a high mass activity of 1.08 A mgPt-1 in a PEMFC cathode with TMA+-COFs. Our work provides an alternative avenue to conventional catalyst engineering through the rational design of advanced composite ionomers for high-performance, low-Pt PEMFCs.

Electrosynthesis of organic amino acids from inorganic nitrogen feedstocks offers a new route to expand the synthetic boundaries of biologically relevant C-N molecules. However, the desired organic C-N coupling pathway is kinetically suppressed by the competing inorganic ammonia (NH3) pathway, rendering selective amino acid electrosynthesis intrinsically challenging. Here, we uncover that this bottleneck originates from the uncontrollable gatekeeping intermediate, hydroxylamine (*NH2OH), at the decisive branching point. To address this challenge, we develop a new programmable reaction-network bifurcation (PRNB) strategy, enabled by an atomically precise dual-site metallene, which directs the reaction bifurcation of *NH2OH from hydrogenation to C-N coupling. As a result, the system reverses the product selectivity, allowing the coupling product to outperform NH3 by a factor of 28.5. This shift further achieves glycine synthesis with a high Faradaic efficiency of 83.2% and a formation rate exceeding 885 mmol/gcat/h, sustained over 225 h and enabling gram-scale synthesis. Mechanistic studies reveal that dual sites reprogram the relative bonding preference of *NH2OH, making C-N coupling dominant for oxime formation. In situ spectroscopy and kinetic isotope measurements further reveal that dual sites reorganize an ordered interfacial H2O network that lowers the hydrogen-transfer barrier by more than half, enabling rapid oxime hydrogenation and high-rate glycine production. The efficient synthesis of diverse amino acids, including alanine, glutamate, and leucine, further underscores PRNB as a general paradigm for controlling reaction-network bifurcations in complex chemical synthesis.

With the rapid growth in energy demand, designing a novel hybrid battery system has become increasingly important. It is critical to reveal the coupling mechanisms of intercalation-conversion hybrid cathodes and provide an in-depth understanding of structure-performance relationships for the electrochemical energy storage devices with high energy density. In this study, a hybrid cathode that combines intercalation-type LiNixCoyMn1-x-yO2 (NCM) with conversion-type oxygen (O2) is proposed. Using in situ electrochemical atomic force microscopy (EC-AFM), we elucidate that the overlithiation of the NCM cathode enhances electronic conductivity and exposes abundant active sites during discharge, thereby inducing the formation of Li2O2. Electrochemical tests demonstrate that the contributions of intercalation and conversion reactions to capacity are rate-dependent, with lower rates favoring the intercalation-dominated electrochemical process. Further scanning transmission electron microscopy characterization indicates that, during prolonged cycling, oxygen vacancies in the NCM intercalation-type cathode serve as preferential sites for the conversion-type Li-O2 intermediates, significantly enhancing the cycling stability of the battery. Ultimately, by optimizing the mass ratio between the intercalation and conversion cathodes, an enhanced cycle stability is achieved. This study offers valuable insights into modulating battery performance through multimechanism reactions in hybrid battery systems.

While phenolic compounds are recognized as key atmospheric precursors of brown carbon (BrC), the mechanisms governing their interfacial transformation into BrC aerosols, particularly at the microdroplet air-water interface (AWI), remain incompletely characterized. This study investigated the photolysis of phenolic compounds in microdroplets under UV irradiation, revealing a transformation efficiency 2 orders of magnitude higher than that in bulk solutions. Through integrated Fourier transform ion cyclotron resonance mass spectrometry, liquid chromatography-mass spectrometry, and fluorescence excitation-emission matrix spectrum, we identified interfacial-confined oligomerization as the dominant pathway generating BrC with oligomer characteristics. Multiscale theoretical simulations unveiled that the AWI functions as a key mediator through a synergistic mechanism: it not only drives the spontaneous accumulation of phenols at the interface, but also enhances their photon absorption efficiency via asymmetric interfacial H-π hydrogen bonding, as evidenced by a critical 24.7% increase in the molar extinction coefficient at 298 nm. Together, these dual effects synergistically facilitate photon capture and subsequent phenoxy radical generation. Our results establish the AWI as photochemical nanoreactors that fundamentally alter atmospheric BrC formation kinetics, providing a mechanistic framework to reconcile field observations of rapid aerosol aging under humid conditions, while challenging current model assumptions about phenolic transformation time scales.

Nonoxidative ethane dehydrogenation (NOEDH) is a carbon efficient but thermodynamically severe route for ethene production. Solar-driven NOEDH offers a promising alternative, yet achieving both high activity and high ethene selectivity over noble metal-free catalysts without external heating remains unresolved. Here, we reported that Ti3+-O acid-base pairs on reduced rutile TiO2 enabled highly efficient full-spectrum solar-driven photothermal NOEDH without any external heating. The optimally reduced TiO2 at 750 °C delivered an ethene production rate of 392.0 mmol g-1 h-1, which was 1107 times higher than that of pristine TiO2 without reduction pretreatment. The high activity with a C2H4 selectivity of 94.9% surpassed the thermodynamic equilibrium limit and outperformed previously reported systems. Comprehensive characterizations identified surface Ti3+ sites adjacent to lattice oxygen as Lewis acid-base pairs that enhanced light absorption, promoted charge carrier separation, and directly participated in the C-H bond cleavage. Photogenerated electrons also preferentially accumulated on the coordinatively unsaturated Ti3+-O sites, which weakened ethene adsorption, thereby accelerating product desorption and suppressing deep dehydrogenation and coke formation. The synergy between photogenerated hot carriers and localized photothermal heating lowered the apparent activation energy from 157.6 kJ mol-1 in the dark to 75.0 kJ mol-1 under illumination. This work establishes surface acid-base pairs on noble metal-free catalyst as a powerful platform for sustainable light-driven alkane upgrading.

Molecules derived from lignocellulosic biomass are oxygenates with multiple oxygen-containing functional groups, such as hydroxyl and carbonyl groups. Therefore, the ability to selectively reduce a specific oxygenate group is essential for the reductive upgrading of such molecules. Previous studies on electrochemical biomass conversion have shown that alcohol hydrogenolysis, which involves cleavage of the σ(C-Oalcohol) bond, is extremely challenging for furfural and 5-hydroxymethylfurfural (HMF) derivatives, including furfuryl alcohol, 5-methylfurfuryl alcohol (MFA), and 2,5-bis(hydroxymethyl)furan (BHMF). In contrast, HMF itself undergoes alcohol hydrogenolysis relatively easily in acidic aqueous media. Considering that the only structural difference between HMF and BHMF or MFA is the presence of a carbonyl group, this observation raises the question of whether the carbonyl group in HMF facilitates alcohol hydrogenolysis. In this study, we designed systematic experiments to provide a coherent explanation of when and how a carbonyl group enables hydrogenolysis of a copresent alcohol group. Specifically, we show that alcohol hydrogenolysis in HMF proceeds via reduction of the carbonyl group to a ketyl radical, followed by a spin-center shift (SCS) through extended π conjugation. We also elucidate the effect of pH on the selectivity between carbonyl hydrogenation and alcohol hydrogenolysis, both of which share the ketyl radical intermediate. This mechanistic understanding enhances our ability to predict and control alcohol hydrogenolysis in the reductive upgrading of biomass-derived oxygenates.

Altermagnets are symmetry-defined magnetic phases that combine momentum-dependent spin splitting with zero net magnetization, offering promising opportunities for spintronics. However, their realization is strongly constrained by rigorous symmetry requirements. Exploiting the shared antiparallel magnetic order and vanishing net magnetization between antiferromagnets and altermagnets, we propose a general chemically driven strategy based on asymmetric ligand modification to transform pristine two-dimensional antiferromagnetic metal-organic frameworks into altermagnetic candidates. Using chromium phthalocyanine (CrPc) as a proof-of-concept model, we show that asymmetric modification lowers the local site symmetry at magnetic Cr centers and generates momentum-dependent spin splitting and anisotropic spin densities, as revealed by first-principles calculations. Oxygen-modified CrPc derivatives further illustrate the chemical tunability of this symmetry-control principle. Our work expands the design space of organic altermagnetic candidates and establishes a chemically grounded route for engineering symmetry-governed magnetic functionality in reticular materials.

Alkenes serve as fundamental motifs across natural products and synthetic molecules, yet efficient, mild, and versatile olefination strategies remain in demand. Nitroalkanes, renowned for their broad reactivity as nucleophiles or corresponding radicals, still offer untapped potential in photocatalysis. Here, we report a unified, photocatalyzed generation of α-nitroalkyl radicals via oxidation of simple, nonprefunctionalized nitronates, followed by addition to another nitronate (formal homo- or cross-coupling) and subsequent double denitration to furnish alkenes. This transformation leverages both the pro-nucleophilic and pro-electrophilic nature of nitroalkanes, challenging the classic McMurry-type coupling protocol. Moreover, the synthetic manifold is scalable and demonstrates its applicability by synthesizing medicinally relevant Combretastatin and lignan-type cores.

Despite their centrality in molecular design, stereodefined tri- and tetrasubstituted alkenes remain challenging to access, as most olefinations favor lower substitution and fail under sterically congested settings. Herein, we report the photoinduced cross-denitrative olefination of nitroalkanes to afford tri- and tetrasubstituted alkenes. Visible light excitation of in situ-generated nitronates promotes a photo-stitching event via denitrative cross-coupling of two nitroalkanes. The transformation tolerates a variety of functionalized nitroalkanes, including carbonyl- and heterocycle-containing substrates, complements metathesis and carbonyl olefination, and scales efficiently. Mechanistic studies support a photoinitiated and photopropagated nucleophilic-radical substitution and radical-chain elimination sequence in which nitronates function as photoreductants to generate radical-anion intermediates that undergo a subsequent photodriven β-elimination. These findings establish a previously inaccessible light-driven elimination process for radical-mediated olefination from readily available building blocks.

Molecular recognition is governed not only by the structural complementarity of the final complex, but by the kinetic pathway through which it forms. Polyubiquitin chains, in which sequence-identical domains are covalently linked yet must be discriminated by dedicated receptors to encode distinct cellular signals, exemplify this challenge. For NMR relaxation dispersion studies of such systems, spectral overlap between identical domains prevents conventional uniform isotope labeling from resolving the per-domain exchange contributions. Here we show, using domain-selective 15N labeling combined with R2 relaxation dispersion, that the binding of linear (Met1-linked) diubiquitin to HOIL-1L NZF proceeds through an apparent three-state pathway as detected by relaxation dispersion, in which rapid ligand-dependent pre-equilibration populates a conformationally preorganized intermediate that is selectively captured by NZF in a slower, chain-type-selective step. This kinetic hierarchy offers a mechanistic basis for understanding the discrimination between linear and Lys63-linked ubiquitin chains that static structures alone cannot reveal. This strategy should be broadly applicable to multidomain recognition systems─including epigenetic reader complexes and multivalent signaling adaptors─where the pathway between known structural end points remains hidden.

ADP-ribosylation (ADPr), long recognized as a canonical protein post-translational modification, has recently expanded to include targeting nucleic acids, uncovering a diverse landscape of noncanonical biological functions. Emerging evidence suggests that ADPr at the 5'-phosphate terminus of DNA is implicated in the DNA damage response, yet understanding its precise molecular function has been hampered by the lack of structurally defined chemical probes. Here, we report the stereoselective synthesis of deoxynucleotide-phospho-ADPr (dN-P-ADPr) probes, representing native fragments of terminal DNA-ADPr. Our strategy leverages a mild, stereocontrolled glycosylation to construct the challenging ribosyl-phosphate linkage, followed by P(III)-P(V) coupling to establish the pyrophosphate bridge. This robust toolkit enabled the systematic biochemical profiling of DNA-ADPr hydrolases across diverse kingdoms of life. Remarkably, using these newly developed probes, we uncover hydrolases across the diversity of life capable of reversing ADPr modifications at phosphorylated DNA ends. We further show that these enzymes exhibit an absolute preference for the native-like α-anomer, independent of the identity of the adjacent DNA nucleobase, suggesting that substrate recognition is governed primarily by the ADPr-phosphate linkages rather than the local nucleobase context. Together, these synthetic probes and biochemical insights provide an essential foundation for deciphering the biological landscape of noncanonical ADPr.

Visualizing the coordination environment-dependent synergistic mechanisms that govern the structural stability and adsorption behavior of dual-atom catalysts (DACs) is pivotal for precise catalyst design. However, insights into these mechanisms at the molecular orbital level remain elusive. Herein, we present large-scale density functional theory calculations to elucidate how synergistic effects arise from the combination of d atomic orbitals into molecular orbitals between M1 and M2 sites, with notable variations observed from M1-N3-M2-N3-C to M1-N4-M2-N4-C. We identify an average weakening of M1/M2-N bond strength in M1-N3-M2-N3-C relative to M1-N4-M2-N4-C, which is attributed to a shift from direct dx2-y2 orbital overlap to nitrogen-mediated interactions involving the hybridization of bridge nitrogen 2p orbitals. Using hydrogen as a model adsorbate, we demonstrate that hydrogen adsorption on M1-N3-M2-N3-C shifts from wild modulation via a bridge configuration to mild modulation through an end-on configuration, signifying a selective orbital coupling from dx2-y2 to dz2 orbitals. In contrast, hydrogen adsorption on M1-N4-M2-N4-C exhibits only mild modulation via an end-on configuration. This behavior is ascribed to the symmetry constraints of antibonding (d-d/d*)-p* molecular orbitals near the Fermi level, mediated by nitrogen-mediated dz2-dz2* molecular orbitals. Furthermore, machine learning analyses corroborate these coordination environment-dependent synergistic mechanisms. Our findings provide a comprehensive molecular orbital-level understanding of how the interplay between coordination environments and electronic structures influences the properties of M1M2N6 catalysts, thereby establishing a theoretical framework for enhanced DACs design.

Explorative chemistry in a reaction system composed of NbI4, Li2(CN2), and Li2O has led to the discovery of a number of niobium oxyiodide cluster compounds. During this reaction, the formation of solid phases was detected alongside gaseous phases, resulting in a range of products with cluster cores of varying shapes. After several niobium oxyiodide cluster compounds have already been identified within this reaction system, two additional compounds, Nb6O3I15 and Nb11O6I24, are discovered and structurally characterized by single-crystal X-ray diffraction. Both structures are based on the butterfly-shaped, oxygen-capped niobium cluster [Nb4O], which is extended to larger cluster fragments. The [Nb4O] cluster core in Nb6O3I15 is extended by two [NbO] units to form a three-dimensional framework, and Nb11O6I24 contains two connected [Nb4O] units, which form chiral units within an antiferrochiral hexagonal packing of strings. The striking string-like character of Nb11O6I24 was investigated in terms of its electronic structure and properties. DFT calculations showed Nb11O6I24 to possess a zero indirect band gap, with a pair of 3-dimensional flat bands surrounding the Fermi level. These unusual features of the electronic band structure suggest the presence of strongly correlated intercluster singlet electron states, arising from the helical shape of the clusters, the hexagonal packing of the strings, and the delocalized nature of cluster electron wave functions.