London dispersion drives counterintuitive contraction without strengthening of Cu─O bonds in sterically bulk copper(I) phenoxides, challenging the classical bond-length/strength correlation. Combined crystallographic and computational analyses reveal that dispersion interactions enforce symmetrical geometries and stabilize shortened, weakened bonds through enhanced π- yet diminished σ-bonding, establishing a new paradigm in metal–ligand bonding.

Conventional chemical wisdom holds that shorter bonds of a given type generally exhibit greater strength. Here, we reveal a counterintuitive bonding mode in copper(I) phenoxides, where bulky substituents induce Cu─O bond contraction without concomitant strengthening. X-ray crystallographic analysis shows that increasing steric bulk at ortho positions of the phenolate ligand can shorten Cu─O bonds and promote symmetrical molecular geometries. Combined structural and computational studies demonstrate that London dispersion (LD) between N-heterocyclic carbene ligands and ortho-tert-butyl phenolates plays a crucial role in driving this conformational reorganization. Local energy decomposition analysis quantifies substantial dispersion stabilization (by up to 11.2 kcal mol−1). Notably, natural orbital analysis indicates that the compressed Cu─O bonds exhibit diminished σ-character despite enhanced π-interactions. This LD-induced bond contraction results in overall shorter yet weaker Cu─O bonds than those in less sterically bulk analogues, thereby establishing a different bonding paradigm from the conventional bond-length/strength correlation.

Engineering localized aromaticity in amine-embedded polycyclic aromatic hydrocarbons effectively suppresses molecular vibration coupling and reduces the intensity of shoulder peaks in emission spectra, thereby giving rise to highly efficient yellow and red narrowband fluorophores for the assembly of high-performance organic light-emitting diodes.

The development of narrowband fluorescent emitters remains a long-standing challenge in organic optoelectronics. Herein, we present an aromaticity engineering approach based on a perylene core to construct highly efficient narrowband fluorescent emitters. Replacement of one naphthalene unit with a carbazole moiety enhances the localization of aromaticity, while extension of the π–conjugation further attenuates the aromaticity of the remaining naphthalene ring. This dual modulation effectively suppresses emission shoulder bands, yielding spectrally pure fluorescence. Consequently, the centrosymmetric c-NaDTCz and the axially symmetric a-NaDTCz exhibit sharp emissions at 536 and 600 nm, with narrow full widths at half-maximum (FWHM) of 17 and 30 nm, respectively. When applied in OLEDs, the c-NaDTCz-based device displays sharp yellow emission peaking at 548 nm with a high external quantum efficiency (EQE) of 26.1%, while a-NaDTCz delivers narrowband red electroluminescence at 610 nm, achieving a record-high EQE of 27.8% for conventional red fluorescent emitters.

An electrochemical α-C─H functionalization of nitramines enables the synthesis of molecules containing bifunctional energetic heterocycles with promising properties. A telescoped, HNO3-free sequence involving nitration and azolation steps offers a safer, modular, and scalable platform for the synthesis of energetic compounds.

The synthesis of energetic materials (EMs) often involves hazardous reagents and harsh conditions, raising safety and environmental concerns. We herein present an electrochemical method for the ⍺-C─H azolation of nitramines, enabling the integration of nitramines and various nitrogen-rich azoles as dual energetic components within the same molecule. To enhance the practicality of the overall synthesis, we developed a tandem two-step process that transforms free amines into nitramines using stable and readily available reagents, which was complemented by subsequent electrochemical azolation to complete a streamlined, scalable preparation of bifunctional energetic compounds. Finally, a continuous flow system was employed to further improve the practicality of the electrosynthetic method, which substantially reduced electrolyte usage and increased productivity. Computational and experimental data revealed that the introduction of azoles, particularly those with additional nitro substituents, improves the energy density and thermal stability of nitramines. This work provides a proof of concept that the reported electrochemical azolation reaction may not only offer a safer and more sustainable alternative to traditional approaches for energetic material synthesis, but it will also provide a platform for the discovery of novel compounds with favorable energetic properties.

This work proposed a hydrogen-capture strategy to achieve H2-interference-free crystallization of a dense zinc hydroxide sulfate (ZHS) SEI by introducing potassium persulfate to suppress hydrogen evolution reaction (HER). This electron-insulating ZHS layer concurrently inhibits dendrite growth and further HER during cycling, stabilizing Zn anodes for long-cycle aqueous zinc batteries.

Aqueous zinc-ion batteries (AZIBs) are promising high-safety energy storage devices, but their practical implementation has been limited by dendrite growth and hydrogen evolution reaction (HER). Solid-electrolyte interface (SEI) is expected to address these problems. Herein, we revealed that HER results in loose and porous interfacial structure, making the in situ construction of reliable SEI a challenge. Thus, a universal and effective hydrogen atom scavenging strategy is proposed to in situ construct a dense and uniform inorganic SEI by introducing potassium persulfate (PSS). PSS scavenges the adsorbed hydrogen atoms, thus inhibiting HER. Meanwhile, PSS is reduced into SO4 2− and participates in the formation of zinc hydroxide sulfates (ZHS). With no interference of H2 bubbles on ZHS crystallization, an ideal SEI is constructed. This ZHS-SEI exhibits superior electronic insulation, effectively suppressing further HER and Zn dendrite growth during cycling. As a result, the Zn//Zn symmetric cell with PSS can achieve stable Zn plating/stripping for 1882 h at 5 mA cm−2 and 2.5 mAh cm−2 and 650 h at 10 mA cm−2 and 5 mAh cm−2, respectively. The cycling stability of the Zn||NVO full cell is also significantly improved at 5 A g−1. This work provides a novel perspective for stabilizing the zinc anode interface.

Controlling enzyme activity with molecular precision remains a fundamental challenge. Here, we present a DNA-based strategy for the dynamic and programmable regulation of enzyme function in response to arbitrary, user-defined chemical cues. We report the development of single-molecule DNA tweezers (SMDTs)—structures that can be programmed to bind and inhibit enzymes, then release upon sensing specific signals, restoring activity.

Engineering allosteric control sites into enzymes typically requires extensive protein modification. Here, we introduce single-molecule DNA tweezers (SMDTs), which enable programmable, allosteric-like regulation of enzyme activity in response to user-defined chemical cues, without altering the enzyme itself. SMDTs consist of two aptamers connected by a tunable, stimuli-responsive DNA linker. By binding non-covalently to two distinct sites on an enzyme, the SMDT adopts a “pinched” conformation, reminiscent of mechanical tweezers, that inhibits enzymatic activity. Upon exposure to specific molecular triggers, the SMDT undergoes a conformational change that releases the inhibitory aptamer, restoring function. The degree of inhibition and reactivation efficiency can be finely tuned by adjusting the DNA linker's length, sequence, flexibility, and geometry. Operating at nanomolar concentrations, the system exhibits high specificity, capable of discriminating between closely related inputs, including single-base mismatches in nucleic acids. Importantly, SMDTs can be programmed to respond not only to molecular abundance but also to molecular activity. We show the versatility of this platform by regulating enzymes using diverse triggers, including nucleic acids, transcription factors (TATA-binding protein [TBP], cellular myelocytomatosis [c-Myc]), signaling proteins (platelet-derived growth factor [PDGF]), small molecules (kanamycin), and metal ions (Mn2+). These results establish a generalizable framework for designing responsive protein binders that translate molecular recognition into functional outcomes.

This work engineers the CEI via electrolyte design, showing its dual role in K+ desolvation under extreme fast charging (XFC) and in sustaining conductivity and robustness. A polarity gradient CEI, rich in B-F/B-O outside and uniform K2CO3/KF inside, accelerates K+ migration and stabilizes structure. As a result, KFeHCF/graphite full cells achieve faster kinetics and stable interfaces, highlighting CEI tailoring as key for XFC batteries.

Potassium-ion batteries (PIBs) offer an opportunity for superior fast-charging compared to lithium-ion batteries, owing to their faster K+ transport in electrolyte. However, severe side reactions at the cathode electrolyte interphase (CEI), sluggish K+ transport, and cathode structural degradation hinder the development of fast-charging PIBs. Herein, we tailor-design a polarity gradient CEI via an electrolyte additives modification strategy. Specifically, the outer B–F/B–O species assist in withdrawing solvent molecules around K+ during the desolvation process, while abundant K2CO3 and KF throughout the CEI facilitate K+ transport and structural stability. Consequently, the KFeHCF/graphite full cell demonstrates improved charge transfer and diffusion kinetics, with suppressed Fe dissolution, enhancing stability of both the cathode bulk structure and interphase under fast-charging conditions. The full cell with optimized CEI delivers high reversible capacities of 126.5 mAh g−1 at 0.02 A g−1 and 95.8 mAh g−1 at 1 A g−1 (a charging time of 7.5 min for 80% of the capacity), and maintains 67 mAh g−1 at 5 A g−1 as well as good long cycle life. Moreover, it retains 85.1 mAh g−1 and exhibits good rate performance even at –10 °C. Our work reveals the critical role of rationally regulating CEI components and structure for fast-charging PIBs.

At present, industrial production methods, such as the Haber–Bosch (H–B) process using N2 and D2, require harsh reaction conditions and complexity equipment, leading to a high production cost of ND3. This work demonstrates a two-step relay route to produce ND3 by using air and deuterium oxide (D2O) as raw materials, including plasma-driven air-to-NOx conversion and electrocatalytic NOx –-to-ND3 conversion, which can be directly driven by volatile green energy.

Deuterated ammonia (ND3) exhibits growing market demand in the fields of chemical analysis, pharmaceutical industry and semiconductor manufacturing. Currently, industrial production of ND3 relies on harsh conditions and complex processes, leading to high production cost and security risk. Herein, we propose a sustainable relay strategy to produce ND3 by using air and deuterium oxide (D2O) as raw materials, including plasma-driven air-to-NOx conversion and electrocatalytic NOx –-to-ND3 conversion. The insufficient supply of reactive deuterium (*D) leads to sluggish kinetics of electrocatalytic deuterium reaction. The well-designed F modified cobalt (F–Co) catalyst exhibits a remarkable yield of 0.75 mmol h−1 cm−2 and a Faradaic efficiency of 80.43% for ND3 at 200 mA cm−2. The combined results of characterizations reveal that fluorine (F) atom can boost D2O dissociation and suppress competing deuterium evolution reaction, thereby providing abundant *D for deuteration reaction. Notably, a pilot-scale demonstration system, consisting of non-thermal plasma, flow electrolyzer, air stripping and ammonia absorber, is constructed to produce practicable ND3 solution (2.8 wt%) with ∼21.45 mmol h−1 ND3 production capability by using air and D2O as sources.

Atomically dispersed transition metal modified Pt-based bimetallic catalysts were designed and synthesized via the ALD method, which are used to investigate the atomic-level electronic effects of Ni and Fe against Pt in methanol steam reforming (MSR) reaction, which was achieved by combining microscopic and spectroscopic analyses, DFT calculations. Notably, the 10cNi/Pt1/CeO2 catalyst exhibited optimal activity and the lowest activation energies, attributed to moderate electronic modification against Pt.

The electronic effects of bimetallic components in catalysis remain poorly understood. Herein, atomically dispersed transition metal (TM) modified platinum (Pt)-based bimetallic catalysts were designed and synthesized with the atomic layer deposition (ALD) method. Methanol steam reforming (MSR) was selected as a probe reaction to investigate the atomic-level electronic effects of nickel (Ni) and iron (Fe) on Pt species. In situ/ex situ characterizations, isotope labeling, and DFT calculations reveal that different transition metals and ALD cycles tune the Pt electronic structure, significantly affecting catalytic activity. Notably, the 10cNi/Pt1/CeO2 catalyst exhibits optimal electronic modification, achieving the highest MSR and water-gas shift (WGS) conversions and the lowest activation energies. Additionally, kinetic isotope effect studies confirm that hydrogen formation proceeds via methanol dehydrogenation coupled with WGS. These findings provide new insights into electronic modifications at atomic scales within the bimetallic components, offering valuable guidance for the design and development of advanced catalytic systems.

A rare silicon(IV)-based azo compound featuring a Si─N═N─Si linkage was synthesized via the direct reaction of an organoazide with a silaiminyl–silylene precursor. This compound undergoes an unusual CO activation process, resulting in N2 release and complete cleavage of the C≡O bond, forming a Si(II)/Si(IV) product bridged by an oxygen atom and an organic isonitrile.

Silicon-substituted azo compounds featuring Si─N═N─Si linkages remain elusive in main-group chemistry. Herein, we report the synthesis of a silicon-based azo compound generated directly from a mixed-valent silaiminyl–silylene precursor and a bulky organic azide. Unlike classical iminosilane formation, this reaction affords a thermally stable Si(IV)–azo species. Upon treatment with carbon monoxide (CO), this compound undergoes N2 extrusion, complete C≡O bond cleavage, and formation of a formal Si(II)/Si(IV) product in which an oxygen atom bridges both silicon centers. Notably, the transformation incorporates the carbon atom into a DippNC byproduct via ligand rearrangement. A similar transformation occurs upon reaction with Fe(CO)5, wherein N2 release and CO cleavage also occur, but with the resulting Fe(CO)4 fragment coordinating to the silicon center. These results demonstrate a rare example of silicon based azo-mediated small-molecule activation and highlight the potential of silicon-based systems for multi-electron redox chemistry typically associated with transition metals.

Visible light photochemical spin-state switching is achieved through a tailored design. The photoswitching core is substituted with the π-acceptor indanedione resulting in a small optical bandgap in combination with torsional twisting of the substituent. This twisting is essential for the stability of the diradical state as it isolates the spin density in the periphery preventing immediate radical–radical recombination.

Controlling the spin state of a molecule using the spatiotemporal properties of visible light is of interest for spintronic devices in information technology or (bio)medical applications. We, herein, report an all-organic visible light-induced photochromic system than can switch from a diamagnetic (singlet) to a paramagnetic (triplet) state. This is realized by precisely tuning orbital symmetry and internal molecular strain in a [5]helicene scaffold substituted with an indanedione π-acceptor. Irradiation with visible light at cryogenic temperatures gives a kinetically meta-stable paramagnetic diradical state with a solvent-dependent ground-state multiplicity (triplet or singlet), which can be thermally switched back to its initial diamagnetic state.

The fate of polymers in liquid formulations in natural environments has not been extensively researched, in part as a result of incompatible analytical techniques. We show that diffusion NMR spectroscopy can be used to quantify the simultaneous biodegradation of multiple water-soluble polymers with limited sample preparation, measuring the molar mass, and chemical composition of multiple species with no molar mass restriction.

Polymers in liquid formulations result in 36 million tons of waste each year. It is estimated that 13% of these polymers directly enter, and accumulate in, natural environments, however, their fate is poorly understood; in part as a consequence of challenges in characterizing how the polymers biodegrade. Multiple analytical techniques have been used to quantify polymer biodegradation but require extensive sample preparation and can only measure one species accurately at a time, inhibiting the measurement of water-soluble polymer mixtures. Here, we report the application of diffusion nuclear magnetic resonance spectroscopy as an alternative method to enable the facile monitoring of polymer biodegradation. This technique uniquely aids the understanding of biodegradation mechanisms, by measuring chemical as well as molar mass changes, concurrently, for both the polymer and degradation products. Furthermore, the ability to detect and measure the molar mass of multiple separate species enables the measurement of simultaneous biodegradation of polymer mixtures, including polymers with different chemical structures but the same molar mass.

We report the formation of a quasi-two-dimensional interconnected amine functionalized nanofiber network at a gas–liquid crystal interface by chemical vapor polymerization. The network forms via an interfacial phase separation pathway, revealing that the range of morphologies accessible via chemical vapor polymerization into liquid crystal is much greater than previously understood.

We report that chemical vapor polymerization (CVP) of aminomethyl[2.2]paracyclophane into nematic liquid crystal (LC) films (thicknesses of 18 µm) yields quasi-two-dimensional, sub-micron thick nanoporous polymer networks consisting of interconnected amine-functionalized nanofibers/nanowalls (widths of 30 ± 1 nm). We establish that the polymer networks form at the free surface of the LC films with thicknesses ranging from 79 ± 5 to 280 ± 14 nm and nanoscopic pores tunable via the choice of LC and monomer loading. Structural analysis using electron microscopy reveals the networks to possess morphologies ranging from open bicontinuous-like to cellular foam-like structures which, along with optical observations and molecular dynamics (MD) simulations, supports a synthesis pathway involving an interface-confined phase separation. MD simulations provide further insight into the atomic-scale processes determining the synthesis pathway, including the role of reactive precursor chemistry (e.g., hydroxymethyl[2.2]paracyclophane versus aminomethyl[2.2]paracyclophane versus [2.2]paracyclophane) in defining the nanostructure of the polymer product. Fluorescence and X-ray photoelectron spectroscopy confirm that the nanofiber sheets are decorated with primary amine groups, permitting covalent functionalization of the surfaces of the nanosheets. Finally, we show how the nanosheet synthesis can be integrated with existing membrane technology, illustrating the potential utility of the nanoporous sheets in a range of contexts, including filters, separators, and heat exchanger surfaces.

Fused B-N coordinated organic NIR phosphors (TPP-BN/BF) with 819 nm emission and 28.6 ms lifetime are synthesized. PMMA-b-PEG nanoengineering yields nanoparticles (PNPs) with five-folds enhanced afterglow. A GrB-responsive nanoprobe (Q-BFNP) leveraging peptide–PRET enables tumor immune monitoring with a 216.4 signal-background ratio, advancing real-time, high-contrast bioimaging, and programmable immunity assessments via molecular-to-nanoscale RTP design.

Organic near-infrared (NIR) room-temperature phosphorescent (RTP) materials hold great potential for bioimaging due to their ability to eliminate background noise and tissue autofluorescence. Here, we synthesized octa-ring fused RTP molecules (TPP-BN and TPP-BF) with B─N coordination bonds via a two-step reaction, enabling NIR phosphorescent emission at 819 nm and a 28.6 ms lifetime. Using PMMA-b-PEG as host and surfactant to stabilize the RTP molecules, we fabricated PMMA-b-PEG based nanoparticles (PNPs) with five-fold brighter afterglow than conventional F127-based methods (FNPs). We further developed a granzyme B (GrB)-responsive nanoprobe (Q-BFNP) that achieves specific and quantitative detection. In vivo studies demonstrated their ability to monitor and distinguish tumor immune response with the signal-to-background ratio (SBR) as high as 216.4. This study provides a new method for constructing NIR organic RTP probes and advances applications of RTP materials in real-time, high-contrast bioimaging and tumor immune monitoring.

A β-secretase-responsive immunotherapeutic agent can synergistically target amyloid-β (Aβ) pathology and innate immunity, achieving a heightened efficacy for Alzheimer's disease (AD) treatment while reducing the side effects associated with conventional antibody therapeutics.

Recent progress in antibody-based immunotherapies for Alzheimer's disease (AD) brings a sense of cautious optimism after years of setbacks. However, these approaches remain constrained by suboptimal pharmacodynamics, modest clinical benefits, and pro-inflammatory adverse effects. Here, we develop a β-secretase-responsive immunotherapeutic agent (ATExo-cL-aA) that synergistically targets amyloid-β (Aβ) and neuroinflammatory response, achieving heightened efficacy while reducing the side effects associated with conventional antibody therapies. After intranasal administration, ATExo-cL-aA actively migrates to AD brains. Upon cleavage by overexpressed β-secretase, ATExo-cL-aA releases aducanumab antibody (aA) and exosomes derived from Aβ antigen-specific Tregs (ATExo), which jointly manage Aβ and inflammatory microglia, thereby synergistically eradicating Aβ and reducing pro-inflammatory responses. In AD mouse models, ATExo-cL-aA demonstrates efficient brain accumulation, robust Aβ removal, microglial normalization, neuroinflammation attenuation, and synaptic preservation, ultimately leading to improved cognitive function. These findings highlight ATExo-cL-aA as next-generation immunotherapeutics that transcend the limitations of conventional antibody-based treatments for AD.

This study designed cyclodextrin and adamantane derivatives that respectively targets the endoplasmic reticulum and mitochondria, achieving precise spatial manipulation at the organelle level through molecular recognition. This approach selectively induced abnormal ER-mitochondrial connections and ultimately led to strong immunogenic cell death. This supramolecular recognition-based strategy provides a new perspective for precision medicine.

Organelles maintain cellular homeostasis through highly specialized division of labor, dynamic interactions, as well as extensive inter-organellar information exchange, thereby ensuring the physiological functions of organisms. Although functionalized polymers that target a specific organelle to modulate or disrupt their function have been developed for therapeutic applications, macromolecular systems capable of manipulating two or more types of key organelles remain rare. Here, we designed cyclodextrin and adamantane derivatives that can respectively target endoplasmic reticulum (ER) and mitochondria, to achieve precise spatial manipulation of both organelles at the subcellular organelle level via a specific molecular recognition approach. This approach selectively induced unusual junctions between the ER and mitochondria, disrupting their functional synergy, triggering multiple cellular stress responses, such as Ca2+ homeostasis imbalance, reactive oxygen species (ROS) burst, energy metabolism disorder, and ultimately leading to severe immunogenic cell death (ICD). By converting “cold” tumors into “hot” tumors, this strategy provides a supramolecular perspective for tumor immunotherapy.

Described here is a LaNTMS mediated silylative conversion of primary amides to nitriles under neat reaction conditions. The reaction is highly efficient and selective under such solventless conditions, where all materials are commercially available, demonstrating the robustness and potential of lanthanide heteroatom catalysis.

Efficient, selective, and environmentally benign catalytic nitrile synthesis is attractive for pharmaceuticals, specialty chemicals and materials, and large-scale industrial applications. In this regard, metal-catalyzed silylative conversion of primary amides to nitriles is emerging as a promising approach. This contribution reports the utilization of readily available lanthanide-organic amido precatalysts, Ln[N(SiMe3)2]3, Ln = lanthanide, to selectively convert primary alkyl and aryl/heterocyclic amides having diverse functional groups to nitriles, including pharma building blocks, in high yields using the silane reagents PhSiH3 and TMS-O-[Si(H)(Me)-O-]n-TMS in a solvent-free process. Kinetic and mechanistic data reveal the role of lanthanide amidates as the catalytically-active species, while DFT analysis indicates a catalytic pathway unlike that found in transition metal complex-catalyzed processes. Thus, the lanthanide amidate resting state actively participates in the catalysis, where rate-determining bound amidate silylation is activated by the metal center and influenced by the bound amidate electronic and steric characteristics. DFT analysis of the catalytic cycle reveals that the relative energies of three intermediate endergonic steps, hence the rate-determining step, depends on the silane concentration.

Illuminating the Oxytocin Receptor: Here we present the development of fluorescent peptide tracers for the simultaneous visualization and activation of the oxytocin receptor, an important G protein-coupled receptor involved in health and disease. These tracers are powerful new tools to support various imaging and functional studies across biological systems.

The oxytocin receptor (OTR) regulates critical physiological functions and has been implicated in a range of diseases, including psychiatric and neurodevelopmental disorders such as autism spectrum disorder. However, a lack of reliable molecular tools hampers the progress in understanding OTR's mechanistic roles in (patho)physiological processes. In this work, we addressed this gap and developed potent, selective, and bright fluorescent peptide tracers that enable precise spatial and functional investigations of OTR actions. Our tracers showed efficient OTR labeling, activation, and internalization in cellular bioassays in both live and fixed overexpression and primary cell systems, including those subjected to immunocytochemical protocols, highlighting their versatility as reliable new imaging tools. Additionally, they facilitated single-molecule tracking of OTR with live-cell super-resolution microscopy and were able to separate OTR-positive cells from mixed oxytocin and vasopressin receptor-containing cell populations via fluorescence-activated cell sorting, underscoring their wider scope for live-cell applications. In summary, we developed versatile fluorescent tracers based on the endogenous ligand oxytocin for both live-cell and post-hoc imaging that have additional functional capabilities beyond traditional antibody labeling, offering new avenues to explore OTR's role in health and disease.

Short amyloid peptides can act as efficient catalysts of neurotransmitter degradation, and libraries of short peptides can be used to identify core fragments present in larger proteins that might be linked to neurodegenerative diseases.

We have shown that de novo designed peptides self-assemble in the presence of copper to create supramolecular assemblies capable of carrying out the oxidation of a range of neurotransmitters in the presence of dioxygen and hydrogen peroxide with high efficiency and in a sequence dependent manner. Moreover, these catalytic peptide assemblies are capable of templating melanin production. Guided by the structure activity relationships identified using the model systems we discovered that peptide assemblies formed by fragments of human carbonic anhydrase VII found in the brain also promote neurotransmitter degradation, supporting its role in neurodegenerative disease. Altogether, our results further support the role of metal-promoted catalysis in neurodegenerative disease and will facilitate development of new catalyst nanomaterials capable of promoting oxidative transformation.

A pulsed laser irradiates Ag-coated Co foil to create catalytic zones where irradiated areas convert NO3 − to NO2 − on hexagonal close-packed (hcp)-Co/face-centered cubic (fcc)-Co and non-irradiated regions reduce NO2 − to NH3 on Ag/hcp-Co heterojunctions. *NO2 intermediates shuttle between zones, with charge transfer promoting *NH2 protonation and suppressing the hydrogen evolution reaction (HER). The system achieves 94.8% NH3 Faradaic efficiency (FE) at −0.4 V (versus RHE), showing a new spatial relay catalysis strategy for multi-step electrochemical processes.

Electrocatalytic nitrate (NO3 −) reduction to ammonia (NH3) represents a sustainable strategy for wastewater treatment and green NH3 production; however, its efficiency is limited by sluggish reaction kinetics and the competing hydrogen evolution reaction (HER). Herein, we propose a laser-programmed spatial relay catalysis strategy mediated by migratory *NO2 intermediate on Co─Ag dual heterojunctions. Site-selective laser irradiation of Ag-predeposited Co foil generates spatially segregated interfaces, where hexagonal close-packed (hcp)-Co/face-centered cubic (fcc)-Co heterojunctions facilitate thermodynamically favorable NO3 − deoxygenation, and Ag/hcp-Co interfaces promote kinetically enhanced NO2 − protonation. Operando spectroscopic analysis, combined with electrochemical differential mass spectrometry (DEMS), confirms the migratory relay mechanism involving *NO2 transport between catalytic sites. Density functional theory (DFT) calculations show that interfacial charge redistribution enables distinct catalytic functions at interface sites. The phase-transformation-formed hcp-Co/fcc-Co heterojunctions enhance NO3 − adsorption and reduce deoxygenation barriers, whereas Ag/hcp-Co interfaces suppress HER and promote *NO hydrogenation by lowering the rate-determining *NO→*NOH barrier to 0.25 eV via Fermi-level d-band engineering. This collaborative spatial design reaches 94.8% ± 3.4% Faradaic efficiency (FE) for NH3 in nitrate-to-ammonia electroreduction at −0.4 V (versus RHE), with 92.5% activity retention over 50 cycles. It highlights the promise of interface-driven relay catalysis in complex electrochemical systems and enables scalable electrode fabrication.

A novel electrocatalytic dual hydrogenation method has been developed using hydrazine and cobalt-based catalysts, enhancing continuous biomass conversion to succinic acid with substantial hydrogenation Faraday efficiency (200%) and long durability (200 h, 100 mA) in a membrane-free solid electrolyte reactor. This advancement highlights significant potential for sustainable green chemistry applications.

Production of chemicals from biomass through electrocatalytic hydrogenation shows great potential to reduce environmental impact across various applications in sustainable materials, medicine, food, and more. Particularly, dual electrocatalytic hydrogenation, leveraging concurrent reactions at both anode and cathode stand out with maximized electron efficiency (∼200%) and production yield. However, at higher voltages, anodic hydrogen atoms (H*) tend to revert to protons. This tendency results in challenges such as low conversion rates and selectivity, and difficulties in maintaining continuous production. Herein, by employing hydrazine and water as the hydrogen sources for anode and cathode reactions, respectively, we achieved efficient dual hydrogenation of maleic acid to succinic acid. This approach produces two H* atoms per electron transferred, promoting effective carbon–carbon (C−C) bond formation at both cathode and anode. We further developed a modular, membrane-free solid electrolyte reactor for continuous dual hydrogenation of maleic acid using a commercial cobalt catalyst. By leveraging the hydrazine oxidation and water reduction, the reactor consistently produces succinic acid with a Faraday efficiency of approximately 180% for over 200 h at 100 mA. Our approach shows significant potential for practical applications in green chemistry, particularly in efficient biomass conversion.