We report a highly efficient synthesis of planar-chiral macrocycles via CpRh(III)-catalyzed intramolecular asymmetric [4+2] annulation reaction of imines with alkynes. The atroposelective de novo isoquinoline ring formation was utilized in this process. The detailed mechanistic studies revealed the rate-determining step of the reaction and the origin of enantioselectivity.

De novo formation of the aromatic ring is an attractive strategy for atroposelective synthesis, but its application to planar-chiral macrocycles remains challenging. Herein, we report a rhodium-catalyzed enantioselective synthesis of planar-chiral macrocycles via de novo isoquinoline construction. This method is characterized by high levels of enantioselectivity (up to 96% ee), regioselectivity (up to >20:1 rr), and functional group tolerance, providing a series of isoquinoline-based macrocyclic atropisomers. Furthermore, the synthetic utility of this protocol is validated via a mmol-scale reaction and post-modification process of the product. Mechanistic studies, including deuterium labeling, kinetic isotope effect, and DFT calculations, support C─H bond cleavage as the rate-determining step and elucidate the origin of the stereoselectivity.

A multi-scale structural regulation strategy enables precise tailoring of hard carbon architectures at micro- and nano-scales. The pitch-modulated carbonization directs the self-assembly of polyphosphazene (PZS) precursors into monodisperse microparticles while in situ forming nanoscale short-range-ordered graphitic domains. The resulting hard carbons demonstrate excellent electrochemical performance for sodium-ion batteries (SIBs) under both ambient and subzero conditions.

Hard carbons, despite their cost-efficient production and precursor availability, face critical electrochemical performance constraints from excessive defects, limited closed-pore structures, and poor interfacial stability. Herein, a multi-scale structural regulation strategy is proposed to tailor both micro- and nanoscale architectures of polymer-derived hard carbons for efficient sodium storage under both ambient and subzero conditions. The pitch-modulated carbonization directs the self-assembly of polyphosphazene (PZS) precursors into monodisperse microparticles while in situ forming nanoscale short-range-ordered graphitic domains. The resulting hard carbons integrate enhanced bulk conductivity, abundant closed pores, and defect-tailored low-surface-area microparticles, collectively enabling an inorganic-rich solid electrolyte interphase (SEI), fast Na+ transport, and suppressed side reactions. The optimized sample delivers a remarkable reversible capacity (413.7 mAh g−1 at 0.05 A g−1) with high initial Columbic efficiency (ICE) (87.1%) and excellent rate capability. More notably, it demonstrates high reversible capacity and exceptional cycling stability at −20°C, achieving a remarkable capacity retention of 98.8% after 3000 cycles and highlighting its practical viability under extreme conditions. The sodium storage mechanisms and accelerated kinetics are revealed through various in situ characterizations and computational techniques, providing deep insights into microstructure tailoring of hard carbons for high-performance sodium-ion batteries (SIBs).

This work demonstrates the nontrivial reactivity of pyridine incorporated into a porphyrin framework. The most significant achievement is the contraction of the six-membered ring to a pyrrole ring, which is a phenomenon of great interest to researchers in this field. In addition, under controlled and mild conditions, the reversible formation of C–O bonds and the coordination of the outer gold ion are also observed.

The pyridine contracted to form the pyrrole ring. This transformation belongs to a unique class of reactions with the fundamental characteristic of the cleavage of the aromatic structure. By investigating the unusual coordination chemistry of N-confused pyriporphyrin with silver and gold ions, we observed this process and obtained several complexes that exhibited remarkable reactivity. This includes the reversible cleavage of C–O bonds and the selective demetallation of the outer metal ion.

Weak cation interaction is proposed to mitigate the intrinsic lithium polysulfide parasitic reactivity toward 500 Wh kg−1 long-cycling lithium–sulfur batteries following the lithium bond theory. Ammonium cation with weaker polarizing power than Li+ is introduced to interact with lithium polysulfides, thereby elevating their lowest unoccupied molecular orbital (LUMO) energy levels and suppressing the detrimental parasitic reactions at lithium metal anodes.

Lithium–sulfur (Li–S) batteries hold great potential as high-energy-density energy storage devices, yet their practical application is hindered by rapid cycling failure caused by parasitic reactions between lithium polysulfides (LiPSs) and lithium metal anodes. Inspired by lithium bond chemistry, we herein propose a weak cation interaction strategy as a new molecular design principle to intrinsically mitigate the parasitic reactivity of LiPSs and endow long-cycling Li–S batteries operating at 500 Wh kg−1 level. Specifically, molecular-level interaction regulation is introduced by employing ammonium cation (NH4 +) with weaker polarizing power than Li+ to interact with LiPSs, thereby attenuating their electrophilicity, elevating their lowest unoccupied molecular orbital energy levels, and suppressing the detrimental parasitic reactions with lithium metal anodes. This regulation strategy markedly prolongs the lifespan of Li–S coin cells from 53 to 149 cycles under harsh conditions of using 4.2 mg cm−2-loading sulfur cathodes and 50 µm-thick lithium anodes. More importantly, an 8 Ah-level Li–S pouch cell achieves a high initial energy density of 502 Wh kg−1 and stable 16 cycles. This work establishes a new weak cation interaction regulation strategy following lithium bond chemistry, offering a generalizable route toward long-cycling and high-energy-density Li–S batteries.

An efficient Cu single-atom catalyst (CuN3−C) with polar electron cloud enables high-rate CO2 electroreduction to CH3OH, achieving 80% Faradaic efficiency and 0.57 µmol s−1 cm−2 production rate via enhanced *CO hydrogenation.

Catalysis of the conversion of CO2 from industrial exhaust gases to methanol at dynamically varying concentrations using renewable electrical energy is crucial for reducing CO2 emissions and producing valuable chemical feedstocks. However, the challenges associated with the weak activation of linear nonpolar CO2 molecules and the high energy difference of key proton-coupled electron transfer steps make it difficult for existing catalysts to simultaneously achieve a high current density and a high selectivity. Herein, we report a strategy for regulating electron polarization in a Cu single-atom catalyst (CuN3-C) to achieve efficient electrocatalytic reduction of high- and low-concentration CO2 to CH3OH. For both high-concentration or low-concentration CO2 used as the feedstock, the CuN3-C catalyst achieves a current density exceeding −450 mA cm−2, a Faradaic efficiency of 80% for methanol production, and record-high production rate of 0.57 µmol s−1 cm−2. In situ characterization and theoretical calculations jointly show that strong electron polarization of the CuN3-C catalyst facilitates more effective CO2 activation and preferential *CO hydrogenation toward *CHO and *CHOH. This study provides a strategy for designing highly efficient catalysts for the conversion of CO2 to methanol via electronic polarization modulation.

Embedding atomically precise metal nanoclusters within a protein scaffold induces a metal-dependent evolution from tunneling to band-like charge transport, governed by cluster size, orbital delocalization, and protein-metal electronic coupling.

Protein-templated metal nanoclusters (MNCs) offer a unique strategy for integrating the structural precision of biological scaffolds with the quantum electronic characteristics of atomically precise metallic cores. Despite this promise, the fundamental principles governing charge transport in such biohybrid systems remain limited. Here, we report a systematic investigation of electron transport in Au/BSA-MNCs/Au Nanowire junctions incorporating a series of bovine serum albumin (BSA)-templated metal nanoclusters of copper, silver, and gold (CuNC, AgNC, and AuNC). Incorporation of MNCs yields up to a 17-fold increase in current relative to native BSA junctions. The conductivity follows the trend AuNC > AgNC > CuNC, a disparity that fragment-level Density Functional Theory (DFT) analysis attributes to the greater structural robustness and enhanced orbital delocalization of AuNC and AgNC, which together facilitate stronger electronic coupling with proximal protein residues. Temperature-dependent charge transport measurements (I-V-T) further reveal a systematic evolution from tunneling-dominated to increasingly band-like transport across the BSA-MNC series, governed by the extent of electronic delocalization imparted by the metal core. Collectively, these findings provide molecular-level insight into charge transport in protein-templated MNCs and establish structure-property design principles for the next-generation bioelectronic materials.

A supramolecular adhesive photoinitiator, GuCD⊃BP-SH, overcomes a central dilemma in enzyme therapeutics. The initiator, featuring a guanidinium-modified cyclodextrin (GuCD) host, triggers formation of a semi-permeable polymer jacket directly on an enzyme. This jacket uniquely provides proteolytic resistance and enables direct cytosolic delivery, all while preserving significant catalytic function, thus unifying protection and substrate access.

Enzyme therapeutics require both catalytic activity and efficient cytosolic delivery—yet protective encapsulation typically compromises enzymatic function, while achieving cellular uptake without lysosomal degradation remains challenging. We address this with a rationally designed supramolecular adhesive photoinitiator (GuCD⊃BP-SH) that unifies surface adhesion, radical initiation, and membrane translocation within a single host-guest architecture. Guanidinium (Gu+) motifs on a cyclodextrin scaffold (GuCD) enable non-covalent adhesion to protein surfaces at carboxylate-rich regions; the cyclodextrin cavity hosts a thiol-benzophenone guest (BP-SH) whose photoactivation (365 nm, 60 mW cm−2 for 30 min) initiates localized grafting-from polymerization, constructing a semi-permeable polymer jacket. Applied to β-galactosidase, this yields sub-100 nm multi-enzyme nanoassemblies (containing ∼10 enzymes per particle) retaining ∼30% catalytic activity with exceptional proteolytic resistance: 86% activity retained versus 25% for unprotected enzyme after Proteinase K challenge. The incorporated Gu+ motifs enable efficient, energy-independent cytosolic delivery via membrane translocation, with 91% of cells showing catalytic activity compared to 5% with non-jacketed enzyme. This modular strategy confers protection and cell-penetrating capability onto native biomacromolecules while maintaining catalytic function, eliminating the need for enzyme release—a persistent bottleneck in therapeutic delivery.

This work reports a distinct tunable in-plane birefringence via domain manipulation in a 2D metal halide ferroelectric, which will advance the development of ferroelectric-based photonic devices for data storage and integrated optoelectronics.

Single crystals with tunable birefringence hold an exciting position in optical and photonic devices due to their exceptional ability of light manipulation. Although ferroelectric domains have been utilized to regulate physical properties, studies on tuning their birefringence by virtue of domain structure remain largely scarce. Herein, we have demonstrated the modulation of in-plane birefringence through manipulating domain structures in a 2D metal halide ferroelectric, (2-MBA)2PbCl4 (1, 2-MBA = 2-methylbutylamine), which exhibits a phase transition at 314 K with spontaneous polarization of 1.6 µC/cm2. Crystal 1 exhibits controllable birefringence that can be modified by thermal and optical stimuli; this behavior directly involves with its ferroelectric properties. Notably, we have achieved unusual in-plane birefringence tuning via domain structure, which is further modulated by coupling domain manipulation with heat, light, and mechanical pressure. This work provides a new strategy for controlling birefringence, and advances the development of ferroelectric-based photonic devices for data storage and integrated optoelectronics.

Angewandte Chemie International Edition, EarlyView.

We report a dual chemical looping/catalytic process coupling alkane dehydrogenation with aromatic alkylation over Cu-mordenite, yielding up to 25% alkylated aromatics with >95% selectivity per cycle. In situ NMR, FTIR spectroscopy, and DFT show alkylation proceeds via a π-bound Cu(I)–olefin intermediate and Brønsted acid sites. DFT reveals a low-barrier bifunctional pathway versus prohibitively high barriers for direct Cu(I)-mediated mechanism.

Given the sustained demand for alkylated aromatics and the strained olefin market, there is an urgent need to develop efficient one-step processes for the direct alkylation of aromatics using alkanes instead of olefins. Such technologies offer greater energy efficiency and sustainability by eliminating the need for separate, energy-intensive alkane dehydrogenation steps. In this work, we report a dual chemical looping / catalytic process that couples alkane dehydrogenation with aromatic alkylation over a copper-containing mordenite yielding up to 25% of alkylated aromatics with >97% selectivity per cycle. In situ MAS NMR and FTIR spectroscopies combined with DFT calculations showed that the alkylation of benzene with alkanes proceeds via a π-bounded Cu(I)-olefin intermediate, which subsequently interacts with benzene, catalyzed by Brønsted acid sites, leading to alkylated products that readily desorb from the active material into the gas phase. DFT calculations show that alkylation mediated solely by Cu(I) has prohibitively high barriers (>1.8 eV), whereas a bi-functional pathway involving both Cu(I) and Brønsted acid sites can proceed with significantly lower barrier (0.8 eV) through a concerted C–C bond formation and proton transfer step.

A one-pot enzymatic platform enables the biosynthesis and site-specific incorporation of chalcogen-containing tyrosine analogues (O, S, Se) into proteins in E. coli. Engineered tyrosine phenol lyase (TPL) variants and orthogonal synthetases are combined to expand the genetic code with redox-active residues, paving the way for designer proteins with tunable electronic and catalytic properties.

Expanding the genetic code with unnatural amino acids (UAAs) offers powerful opportunities to engineer proteins with novel redox and catalytic functions, but is often limited by the need for multistep UAA synthesis and inefficient cellular uptake. Here, we report an integrated biosynthetic–genetic incorporation strategy for chalcogen-containing proteins from the respective phenols. Structure-guided engineering of tyrosine phenol lyase (TPL) enabled the enzymatic production of 3-methoxy-, 3-methylthio-, and 3-methylseleno-L-tyrosine (MeSeY) directly in living cells. Using evolved orthogonal aminoacyl-tRNA synthetases, these analogues were site-specifically incorporated into green fluorescent protein (GFP), as confirmed by fluorescence assays, spectroscopy, and mass spectrometry. We further established a one-pot in vivo system that unifies analogue biosynthesis with translation, reducing precursor requirements and cellular toxicity. This work introduces selenium as a genetically encoded handle for protein engineering and establishes a scalable strategy that couples biocatalysis with genetic code expansion to access redox-active designer proteins. Importantly, installation of MeSeY at the GFP chromophore residue Tyr66 provides redox-responsive fluorescence. In a circularly permuted GFP (cpGFP) scaffold, improved chromophore accessibility enables reversible redox switching under H2O2/thiol cycling.

We engineer unsaturated Cu–N3 sites to create local polarized microenvironments on the carbon host matrix, which accelerates iodine redox reaction and suppresses polyiodides shuttling. This work provides a general strategy for rational design of aqueous battery electrodes, bridging atomic-scale chemistry with macroscopic electrochemical performance.

Rational engineering of the local microenvironment in catalytic host materials is pivotal for high-performance zinc-iodine batteries, as it governs iodine species adsorption, accelerates redox kinetics, and suppresses polyiodides shuttling. Herein, we propose a local polarity engineering strategy by incorporating unsaturated Cu–N3 sites into carbon matrix to construct polarized microenvironments and promote iodine redox chemistry. Combined theoretical and experimental analyses reveal that the unsaturated coordination of Cu atoms induces intrinsic local polarity, which enhances charge redistribution, lowers the activation barrier of the I2/I− redox reaction, and strengthens electronic coupling with polyiodide intermediates. In situ UV–vis and Raman spectroscopies corroborate that the Cu–N3 sites effectively immobilize polyiodides, thus mitigating the shuttle effect. As cathode host, the Cu–N3 sites-rich carbon electrode achieves high discharge capacity of 232.2 mAh g−1 at 0.2 A g−1 and exceptional long-term stability with 94.02% capacity retention after 50,000 cycles at 10 A g−1. More importantly, benefiting from its superior catalytic activity toward iodine redox reaction, the Cu–N3 sites-rich carbon enables solar cells to achieve a remarkable power conversion efficiency of 9.14%. This work elucidates a novel design principle for regulating local polarity to propel iodine electrochemistry, offering new insights into the development of advanced iodine-based energy devices.

A unique charge and lattice self-regulation mechanism is unveiled in Cu3PSe4 that drives expedited Zn2+ transport and high-capacity performance. This mechanism originates from phosphorus-induced charge and structural reconfiguration of in situ-formed Cu2Se, triggering a transition from lattice contraction to expansion and thereby enhances capacity and Zn2+ transport kinetics.

Zn–I2 batteries is a promising large-scale energy storage technology, yet conventional Zn metal anode faces challenges including corrosion, dendrite growth, and side reactions, hindering its practical application. Zn2+ host anodes, leveraging the rocking-chair mechanism and inherent polyiodide inertness, offer a potential solution to these issues. However, existing host anodes suffer from sluggish Zn2+ kinetics and low capacity, limiting their compatibility with cathodes. Herein, we report a unique charge and lattice self-regulation mechanism in Cu3PSe4 that drives expedited Zn2+ transport and high-capacity performance. In this configuration, Cu3PSe4 in situ decomposes to P and Cu2Se during initial cycling and Cu2Se provide subsequent capacity. Importantly, phosphorus modulates the Cu2Se lattice, inducing a transition from conventional contraction to expansion during Zn2+ insertion, thereby enhancing ion transport kinetics and capacity simultaneously. Theoretical calculations reveal that P reconfigures the charge distribution and spatial configuration in Cu2Se, reducing Zn2+ diffusion barrier. Consequently, the optimized Cu3PSe4 anode delivers 150.5 mAh g−1 at 20 A g−1, and the assembled Cu3PSe4||I2 cell achieves an exceptional lifespan of 30,000 cycles at 9 mg cm−2 with a low N/P ratio of 1.1, demonstrating superior stability. This work provides a novel system of corrosion-resistant anode for high-performance and metal-zinc-free zinc–iodine batteries.

An acyltransferase from Chromobacterium sphagni (CsATase) was identified that catalyzes the regioselective formylation of resorcinol substrates. The formylation of substituted resorcinol derivatives yielded mono-formylated products with up to 99% conversion and up to 74% isolated yield. The structure of CsATase was elucidated by X-ray crystallography, providing insight into its active site.

Although aromatic formylation reactions are highly valuable from a synthetic perspective, a biocatalytic version has not yet been reported. Here, the cofactor-independent multimeric three-component acyltransferase from Chromobacterium sphagni (CsATase) was identified to enable the nonnatural promiscuous regioselective C-formylation of polyphenolic substrates, especially resorcinol derivatives, and thus extending the reaction scope of acyltransferases. Formylation of 4- and 5-substituted resorcinol derivatives gave access to regioselectively mono-formylated products with up to 99% conversion and up to 74% isolated yield. Formylation of phloroglucinol led to the di-formylated product with 99% conversion, outperforming chemical methods. Structural analysis of CsATase by X-ray crystallography provided insights into its active site.

Pyrimidine-rich ssDNA flaps on the T7 promoter inhibit T7 RNA polymerase (T7RP) transcription. Leveraging this pyrimidine bias, we developed DNAzyme- and MNAzyme-mediated flap promoter induced transcription control (D-FIT and M-FIT) systems. These platforms enable regulated transcription and sequence-specific detection, highlighting the programmable potential of T7RP pyrimidine bias.

The growing success of RNA-based therapeutics has emphasized the need for precise and programmable RNA synthesis platforms. T7 RNA polymerase (T7RP) is widely utilized for in vitro transcription; however, most existing regulatory strategies rely on auxiliary proteins or chemical modulators. Here, we investigated whether transcription can be regulated solely through nucleic acid sequences. Specifically, we evaluated the effects of single-stranded DNA flap sequences appended to the 3′ end of the non-template strand of the T7 promoter, termed the flap promoter, on transcriptional efficiency. Remarkably, we observed a sequence-dependent inhibitory effect, wherein flaps enriched in pyrimidines (cytosine and thymine) significantly suppressed T7RP-mediated transcription. Leveraging this intrinsic sequence preference, we developed two novel transcription control platforms, D-FIT (DNAzyme-mediated Flap promoter Induced Transcription control) and M-FIT (MNAzyme-mediated Flap promoter Induced Transcription control) that enable precise regulation of T7RP activity without the need for auxiliary proteins or chemical agents. These findings uncover a previously unrecognized sequence-specific regulatory mechanism of T7RP and establish a new framework for the rational design of programmable RNA synthesis systems, with broad potential applications in RNA therapeutics and diagnostics.

A molecular manganese electrocatalyst enables the direct electrochemical capture and conversion of dilute CO2 (1% – 0.2%) to CO with nearly unit Faradaic efficiency, achieving high efficiency even at atmospheric concentrations (420 ppm). By bypassing energy-intensive pre-concentration steps, this integrated approach highlights a sustainable pathway for valorizing dilute CO2 streams directly into chemical fuels.

The conversion of low-concentration CO2 streams into fuel is highly desirable for industrial applications, avoiding energy-intensive CO2 capture and concentration. Here, we report a highly active molecular electrocatalyst, fac-[Mn(CO)3(bis-MeNHC)(MeCN)]+ (1-MeCN+ ), which enables the direct electrochemical reduction of near-atmospheric CO2 concentrations to CO with up to 100% Faradaic efficiency. Voltammetric analysis at varying CO2 concentrations reveals a clear transition between distinct kinetic regimes, shifting from pure kinetic control to a regime dominated by CO2 depletion. Kinetic analysis in the 5%–100% CO2 range reveals a first-order dependence on substrate concentration. Infrared spectroelectrochemistry confirms that the electrogenerated anionic catalyst remains active under extremely diluted CO2 conditions. Computational modeling further supports that the CO2-to-CO conversion mediated by the doubly reduced species is kinetically accessible at atmospheric CO2 levels. This work demonstrates molecular electrocatalysis even at CO2 concentrations as low as 420 ppm (i.e. atmospheric CO2 partial pressure).

Angewandte Chemie International Edition, EarlyView.

Created in BioRender. Bohg, C. (2026) https://BioRender.Com/ vi9hi4f.

Rhomboid proteases are a mechanistically unique and evolutionarily conserved protein family. Despite their pharmacological relevance, the development of selective inhibitors has lagged behind that of soluble proteases. Using a high-throughput screen, novel chemotypes with selective inhibitory activity were identified. Biochemical assays, solid-state NMR, and molecular docking were used to define inhibitor binding sites and modes.

Rhomboid proteases, a class of intramembrane proteases characterized by a Ser-His catalytic dyad, have recently emerged as promising therapeutic targets. While inhibitors for soluble serine proteases have been extensively studied, the spectrum of potent rhomboid protease inhibitor chemotypes is limited to active-site targeted nucleophiles. To address this limitation, we conducted a high-throughput screen of over 68,000 compounds targeting the E. coli rhomboid protease GlpG, using a fluorescent liposome-based assay. A selection of 326 inhibitory compounds was evaluated in a subsequent IC50 screen against two variants of GlpG (core domain and full length), a soluble serine protease (chymotrypsin), as well as the human mitochondrial rhomboid PARL. Of these, the selective inhibitory effects of 2 compounds and their analogues on GlpG were confirmed through further biochemical and biophysical characterisation, molecular docking, and solid-state NMR spectroscopy. This study paves the way for developing small-molecule tool compounds and drug-like molecules targeting rhomboid proteases.

A novel class of proton-activated artificial ion channels was developed by integrating self-assembled peptide chains into a pH-responsive 2,2′-bipyridine scaffold. Protonation induces a conformational switch in the channel-forming units, promoting one-dimensional self-assembly and subsequent hydrophobic packing into functional channels that selectively kill cancer cells while sparing normal cells.

Proton-activated ion channels mediate ion transport in response to extracellular acidification, enabling cellular adaptation to acidic microenvironments. Despite their biological importance, mimicking proton-activated functionality in artificial ion channels remains a significant challenge. Here, we present a novel class of proton-activated artificial ion channels built from self-assembled peptide chains integrated into a pH-responsive 2,2′-bipyridine scaffold. Protonation induces a conformational switch in the channel-forming units, promoting one-dimensional self-assembly and subsequent hydrophobic packing into functional channels capable of transporting small molecules. As extracellular pH decreases from 7.4 to 6.5, C-FF exhibits a 10.3-fold enhancement in cytotoxicity against human colorectal carcinoma cells, boosting an IC50 of 2.8 µM, mediated through apoptosis induction and cell cycle arrest resulting from disruption of the autophagic process. Significantly, C-FF demonstrates exceptional selectivity for cancer cells, achieving a selectivity index of 8.5, surpassing that of doxorubicin by one order of magnitude while maintaining comparable potency, highlighting its potential as a pH-responsive platform for selective anticancer therapy in acidic tumor microenvironments.

Light-induced modulation of the local microenvironment on the surface of Bi-MOF enhances H+ supply capacity and the LMCT effect, thereby facilitating PCET process. The cation hydration effect disrupts HB networks to construct N2 transport channels. These strategies synergistically achieve a dynamic balance among N2 adsorption and activation, proton supply capacity and proton transfer, thus promoting the pNRR process.

For photocatalytic reduction of dinitrogen in aqueous solution, water plays an important role as not only a reactant to supply protons via the water oxidation reaction, but also a solvent, which cannot be neglected. At the interface between the catalyst surface and local water molecules, modulation of the hydrogen bonds (HBs) is critical for improving the production rate of ammonia. Herein, both roles (i.e., reactant and solvent) were balanced through the formation of an interfacial HB network between organic ligands of Bi-MOFs and water with the aim of accelerating water oxidation to produce more protons and facilitating the adsorption of N2 as well as the release of free water molecules. With this approach, the ammonia synthesis rate reached 258.86 µmol·g−1·h−1 at ambient conditions. As demonstrated, the empty 6p orbitals present in Bi3+(6s26p0), can accept electrons from the ligands due to the ligand-to-metal charge transfer (LMCT) effect. These electrons are then transferred to the π* antibonding orbitals of N2, thus significantly weakening the N≡N bond. The photogenerated holes on the ligands oxidize hydrogen-bonded water molecules, producing more protons, which can further promote the critical process, namely the proton-coupled electron transfer (PCET), for the multi-step hydrogenation of N2. Therefore, the dynamic balance among N2 adsorption and activation, proton supply capacity, and proton transfer was achieved through a local microenvironment modulation strategy on MOFs. As a further proof, a phototactically produced NH4 + solution with a concentration of approx. 200 mg·L−1 was concentrated and used as a fertilizer. Overall, this work provided a new design strategy for the photocatalytic reduction of N2 to produce ammonia on MOFs by elucidating the key role of the HB network.