Haifeng Lv

Solar-driven overall water splitting provides a route for converting solar energy into chemical fuels, but its realization in porphyrin-based metal–organic frameworks (PMOFs) is limited by the difficulty of coupling reduction and oxidation chemistry within a single framework. Herein, first-principles calculations reveal a spatial separation of the frontier electronic states in two-dimensional M–Cu PMOFs (M = transition metal): the conduction-band edge is predominantly associated with the Cu2(COO)4 paddle-wheel node, whereas the valence-band edge is mainly localized on the porphyrin linker. Combined with site-resolved reaction thermodynamics, this electronic partitioning predicts spatially distinct regions for the hydrogen evolution reaction and oxygen evolution reaction. Systematic screening of 27 M–Cu PMOFs identifies Rh–Cu PMOF as the only candidate satisfying the adopted thermodynamic criteria for both half-reactions, with an idealized upper-bound solar-to-hydrogen efficiency of 15.31% under the adopted spectral model. Sure independence screening and sparsifying operator (SISSO) analysis further identifies total magnetic moment, electronegativity, group number, and d-electron count as physically interpretable descriptors of property variations within this M–Cu PMOF series. These results highlight cooperative linker-node electronic regulation as a computational design principle for porphyrin-based frameworks with spatially differentiated redox functions.

Quantum organic–inorganic superlattices, constructed by vertically stacking two-dimensional inorganic crystals and organic molecular layers, offer a powerful platform for encoding emergent electronic states through an interfacial design. However, the precise layer engineering of such hybrid architectures, particularly the deterministic control over vertical stacking periodicities, has remained elusive because of the absence of a predictive thermodynamic framework governing the staging effect in hybrid systems. Here, we demonstrate that thermodynamic design, based on the quantitative competition between intercalant chemical potential and host elastic deformation energy, provides a principled route to programmable layer engineering of organic–inorganic superlattices. By precisely modulating the chemical potential of the intercalant, we achieve selective access to stage-1 intercalation (alternating 1-layer (1L) molecule/1L-SnSe2) and stage-2 intercalation (alternating 1L-molecule/2L-SnSe2) configurations with high structural fidelity. Atomic-resolution imaging reveals long-range periodic order across both staging phases, while angle-resolved photoemission spectroscopy reveals that the engineered layer sequence directly governs the interfacial charge transfer and electronic band structure evolution. The resulting superlattices exhibit stacking-dependent carrier densities and programmable superconducting transitions, establishing the layer sequence as a synthetic handle for quantum functionality. This work establishes thermodynamic design as a guiding principle for the rational layer engineering of quantum-hybrid solids.

Hydrogen peroxide (H ₂ O ₂ ) is a versatile green oxidant and energy carrier, yet its solar production from water and oxygen is limited by the kinetic mismatch between water oxidation and oxygen reduction, as well as insufficient coordination between photogenerated electrons and proton delivery. Here, we report conjugated bithiophene frameworks (CBFs) that integrate molecularly differentiated redox motifs with alkynyl‐regulated electron–proton coordination for efficient H ₂ O ₂ photosynthesis. Progressive extension of alkynyl bridges from CBF‐TB to CBF‐TDB induces an intraframework excited‐state redox polarization that biases photogenerated holes toward benzene/alkynyl motifs and electrons toward thiophene units, facilitating water oxidation and oxygen reduction, respectively. Simultaneously, the alkynyl‐rich framework organizes interfacial water into a hydrogen‐bonded network that facilitates proton delivery to the oxygen reduction interface. The resulting synergy between directional charge transport and localized proton supply promotes proton‐coupled two‐electron oxygen reduction to H ₂ O ₂ . Consequently, CBF‐TDB achieves a solar‐to‐chemical conversion efficiency of 1.01% under simulated solar irradiation, more than 4 times that of the alkynyl‐free analogue CBF‐TB (0.21%). This study establishes the coordinated regulation of excited‐state charge polarization and interfacial proton delivery as a molecular design principle for efficient H ₂ O ₂ photosynthesis and, more broadly, multistep solar‐to‐chemical conversions.

Hydrogen peroxide (H ₂ O ₂ ) is a versatile green oxidant and energy carrier, yet its solar production from water and oxygen is limited by the kinetic mismatch between water oxidation and oxygen reduction, as well as insufficient coordination between photogenerated electrons and proton delivery. Here, we report conjugated bithiophene frameworks (CBFs) that integrate molecularly differentiated redox motifs with alkynyl‐regulated electron–proton coordination for efficient H ₂ O ₂ photosynthesis. Progressive extension of alkynyl bridges from CBF‐TB to CBF‐TDB induces an intraframework excited‐state redox polarization that biases photogenerated holes toward benzene/alkynyl motifs and electrons toward thiophene units, facilitating water oxidation and oxygen reduction, respectively. Simultaneously, the alkynyl‐rich framework organizes interfacial water into a hydrogen‐bonded network that facilitates proton delivery to the oxygen reduction interface. The resulting synergy between directional charge transport and localized proton supply promotes proton‐coupled two‐electron oxygen reduction to H ₂ O ₂ . Consequently, CBF‐TDB achieves a solar‐to‐chemical conversion efficiency of 1.01% under simulated solar irradiation, more than 4 times that of the alkynyl‐free analogue CBF‐TB (0.21%). This study establishes the coordinated regulation of excited‐state charge polarization and interfacial proton delivery as a molecular design principle for efficient H ₂ O ₂ photosynthesis and, more broadly, multistep solar‐to‐chemical conversions.

Fully compensated ferrimagnets (fFiMs), which combine vanishing macroscopic magnetization with spin-split electronic states, are attractive for stray-field-free spintronics. However, achieving exact moment cancellation typically requires fine control over inequivalent magnetic sublattices, making the rational design of fFiMs a fundamental challenge. Here, we propose a general design strategy for two-dimensional (2D) fFiMs by integrating redox-active noninnocent ligands (NILs) into metal–organic frameworks (MOFs). First-principles calculations demonstrate that fractional metal-to-ligand charge transfer converts NILs from closed-shell linkers into a spin-bearing ligand sublattice that aligns antiparallel to the metal centers, enabling stoichiometric moment compensation. We validated this concept in a family of trigonal 2D chromium MOFs. While the prototype Cr(BTT)2 confirms fully compensated ferrimagnetism, it exhibits intrinsic thermal instability. The modular nature of the NIL strategy allows for chemical refinement, and ligand fluorination (Cr(F-BTT)2) or heavy-chalcogen substitution (Cr(BSeT)2) stabilizes the 2D lattice without disrupting the fFiM ground state. The chemically optimized Cr(F-BTT)2 retains fully compensated ferrimagnetism and exhibits a near-Fermi quasi-Dirac-like band feature with an estimated magnetic transition temperature of 132 K. Extended studies of nitrogen- and phosphorus-based ligands further support the generality and boundary of this approach. These findings establish NIL-directed charge transfer as a chemically programmable handle for engineering 2D-compensated magnets.

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.

Interfacial instability of LiCoO ₂ (LCO) above 4.6 V remains a bottleneck for high‐energy‐density batteries due to the coupled Co dissolution and O release. Here, inspired by mortise‐tenon structures, we propose a dual‐site cooperative anchoring strategy targeting Co and O lattice sites via atomic orbital‐level interactions. Through screening based on electronic structure and geometric compatibility, phenylmethylsulfonyl fluoride (PMSF) was identified as an optimal additive. Owing to its high HOMO level and precise spatial matching, PMSF undergoes site‐specific sacrificial oxidation prioritized at the LCO surface lattice. This dual‐site docking achieves directional orbital overlap with the surface Co and O sites, effectively lowering the activation energy for the formation of a uniform, ion‐conductive, and thin (∼5 nm) cathode electrolyte interphase. The resulting interphase acts as a robust chemical shield that suppresses Co dissolution and O loss simultaneously. As a result, LCO half‐cells with 0.3 wt% PMSF retained 61.9% capacity after 200 cycles at 4.8 V. Moreover, 1 Ah graphite||LCO pouch cells maintained 99.5% and 79.6% capacity after 300 and 600 cycles at 4.6 V, respectively. These findings demonstrate that dual‐site anchoring provides a pivotal guiding principle for transitioning from disordered decomposition to controlled, site‐specific interfacial assembly for next‐generation high‐voltage cathodes.

Interfacial instability of LiCoO ₂ (LCO) above 4.6 V remains a bottleneck for high‐energy‐density batteries due to the coupled Co dissolution and O release. Here, inspired by mortise‐tenon structures, we propose a dual‐site cooperative anchoring strategy targeting Co and O lattice sites via atomic orbital‐level interactions. Through screening based on electronic structure and geometric compatibility, phenylmethylsulfonyl fluoride (PMSF) was identified as an optimal additive. Owing to its high HOMO level and precise spatial matching, PMSF undergoes site‐specific sacrificial oxidation prioritized at the LCO surface lattice. This dual‐site docking achieves directional orbital overlap with the surface Co and O sites, effectively lowering the activation energy for the formation of a uniform, ion‐conductive, and thin (∼5 nm) cathode electrolyte interphase. The resulting interphase acts as a robust chemical shield that suppresses Co dissolution and O loss simultaneously. As a result, LCO half‐cells with 0.3 wt% PMSF retained 61.9% capacity after 200 cycles at 4.8 V. Moreover, 1 Ah graphite||LCO pouch cells maintained 99.5% and 79.6% capacity after 300 and 600 cycles at 4.6 V, respectively. These findings demonstrate that dual‐site anchoring provides a pivotal guiding principle for transitioning from disordered decomposition to controlled, site‐specific interfacial assembly for next‐generation high‐voltage cathodes.

The development of spin functionalities depends critically on magnetic materials in which spin states, exchange pathways, and transport properties can be precisely engineered at the atomic level. Reticular chemistry provides a modular and programmable platform to meet this need by enabling rigorous control over the composition, connectivity, and topology within periodic frameworks. At the intersection of these two fields, reticular spintronics exploits chemical precision to systematically modulate spin-active centers and exchange interactions while incorporating stimuli-responsive components for dynamic control. In this review, we discuss how reticular architectures can translate molecular design principles into tunable spintronic behaviors in metal–organic frameworks (MOFs) and covalent organic frameworks (COFs) to highlight complementary design features. By linking microscopic coordination chemistry to macroscopic spin phenomena, these frameworks offer a versatile route to predictable control over spin-polarized transport and collective magnetism. These insights establish a design-oriented framework for engineering spin in reticular framework-based systems and guide the development of chemically programmable spin materials.

Photocatalytic H₂O₂ production from H₂O and O₂ provides a sustainable alternative to the energy-intensive, multistep anthraquinone (AQ) process that relies on metal catalysts (e.g., Pd/Ni). Although many photocatalysts have been explored, achieving high efficiency under sacrificial-agent-free conditions with a rationally defined active site remains challenging. Here, we report an inverse-design strategy for covalent organic frameworks (COFs) based on “boat-like C═N-conjugated fragments” (−C═N–C═N– or −N═C–C═N−) which mimic key AQ reactivity by integrating active molecular fragments into periodic frameworks through a bottom-up approach. First-principles calculations identified 39 molecular fragments, including 36 newly proposed structures, and demonstrated their ability to drive the two-electron oxygen reduction reaction via sequential protonation and electron transfer. Unlike conventional single-property descriptors (e.g., band gap), we introduce a holistic electronic activity descriptor based on density-of-states (DOS) similarity to screen 106 designed COFs. This electronic fingerprint identified 11 candidates with >70% total DOS and >60% carbon partial DOS similarity relative to a high-performance reference. Subsequent Gibbs free-energy analyses predict that 9 candidates can support sacrificial-agent-free H₂O₂ production under visible light, corresponding to a theoretical screening success rate of approximately 81%. Experimental validation included the synthesis of TRI-BIP-TRI (TBiT) via trifluoromethanesulfonic acid-catalyzed cyclotrimerization. Under visible light (>400 nm) in pure water under O₂, TBiT produces H₂O₂ at 3084.27 μmol g^–1 h^–1 without sacrificial agents. These results establish a computation-guided framework for designing COF photocatalysts for sustainable H₂O₂ production.