As a cost-effective and environment-friendly oxide, silica (SiO2) is commonly used as a support for catalyst featuring static active sites. However, achieving accurate interface control on inert SiO2-based catalysts, featuring uniformly dispersed and mobile metal sites, remains a significant challenge. Additionally, the multistep hydrogenolysis of multidimensional N-benzyl compounds under mild conditions continues to attract considerable attention. Herein, a synergistic strategy is proposed to tailor the catalyst interface. The accurately loaded CeOx nanodomains served as a bridge between the inert V-SiO2 supports and the Pd active species. Ultrasmall Pd(OH)2 nanoclusters were uniformly anchored onto the supports due to this bridging effect. Under mild reaction conditions, the catalytic activity outperforms previously reported catalysts in the multi-step hydrogenation debenzylation of hexabenzylhexaazaisowurtzitane (HBIW). With only 0.80 wt parts per thousand palladium relative to HBIW, the turnover number (TON) and yield reach 172.8 and 92.1%, respectively. Experiments and theoretical calculations reveal that the interfacial synergy between highly dispersed electron-deficient Pd species and CeOx nanodomains rich in oxygen vacancies collectively enhance the mobile catalytic reaction. This strategy brings forth a new paradigm in the designing and synthesizing heterogeneous catalysts.

Skeletal editing has emerged as a powerful and innovative tool in organic chemistry, offering an efficient approach to the synthesis of complex molecules. Conventional indole skeletal editing approaches predominantly rely on complex carbene precursors and/or transition-metal catalysis to achieve ring expansion. Herein, we report an electrochemical single-carbon insertion strategy for the skeletal editing of indoles into quinolines, which proceeds without the need for specialized reagents or transition-metal catalysts. The reaction is proposed to proceed via an electrooxidative denitrogenation process, in which in situ formed hydrazones generate reactive carbene intermediates that promote ring expansion. This strategy establishes a new activation platform for skeletal editing chemistry.

Azido energetic compounds are important components of primary explosives because of their excellent initiating ability. However, azido-group installation in energetic molecules usually relies on hazardous reagents such as NaN3. Herein, we report an atom-economical azido-group installation strategy based on an intramolecular Dutt-Wormall-type process that requires neither an external azide reagent nor an additional amine source. Using this approach, azido-containing energetic compound ATPTT was synthesized, showing excellent detonation performance (D-v = 9217 m/s) together with acceptable thermal stability (147 degrees C) and sensitivity (IS = 3.5 J; FS = 40 N). This work offers a new route to azido-functionalized nitrogen-rich energetic heterocycles and highlights its value for the development of high-performance primary explosives.

ABSTRACT Aqueous all‐organic proton batteries promise safe, sustainable, and high‐rate energy storage, but operation under near‐neutral conditions is hindered by low proton activity and competition from nonproton charge carriers. Here, we report a proton capture and relay codesign strategy that enables proton‐dominated charge storage without strongly acidic electrolytes. The electrode pair comprises two N‐centered redox molecules with high proton affinity: an air‐stable preprotonated imine cathode, DCTA‐2H, and a low‐potential azo anode, BCC. The electrolyte is concentrated NH 4 OAc, a near‐neutral proton‐transfer medium in which NH 4 + forms hydrogen‐bonded contacts with imine/azo sites and facilitates interfacial proton transfer rather than being stored predominantly as an intact ion. The resulting BCC||DCTA‐2H full cell delivers a discharge voltage of ≈0.85 V and a capacity of 270.9 mAh g BCC −1 , retains 86.5% of its capacity after 3,000 cycles, and remains operable at −50°C. This work establishes coupled electrode–electrolyte design as a route to near‐neutral all‐organic aqueous proton batteries.

Bridging long-duration electrochemical power delivery with on-demand, ultrafast explosive output within a single material could enable next-generation mission-critical power systems. Here, we report an insensitive yet energetic small molecule, 4,4',6,6'-tetramino(azo)-1,3,5-triazine (TAAT) as a high-performance organic cathode for batteries with dual-mode energy release. Guided by a modular "function-by-design" strategy, TAAT concurrently exhibits low solubility, reversible Li+ storage, triggerable explosive output, and high insensitivity. In lithium batteries, TAAT delivers 215 mAh g-1 with a ≈ 3.0 V discharge plateau and sustains stable cycling over 700 cycles; TAAT||Li pouch cells power a mini quadcopter. Beyond electrochemistry, TAAT exhibits a detonation velocity of 7505 m s-1 and detonation pressure of 18.4 GPa, while remaining thermally and mechanically insensitive (Td ≈ 327 °C; impact >40 J; friction >360 N). The energetic response can be initiated by hot wire, laser, or detonator stimuli. These results establish TAAT as a proof-of-concept dual-mode energy-release material, advancing mission-tailored battery technologies.

Here we report a skeletal-isomeric scaffold design strategy for a fused N-heterocyclic energetic platform based on the dipyrazole[3,4-b;4',3'-e]pyrazine scaffold. This framework preserves planarity, symmetry, and π-conjugation while enabling distinct functionalization. On this basis, DNDP and TNDP were synthesized and characterized. TNDP exhibits a density of 1.97 g·cm-3, a decomposition temperature of 201 °C, and calculated detonation performance of 9501 m·s-1 and 41.1 GPa. The delocalized backbone offsets dense nitro groups, ensuring thermal robustness and high performance.

Direct electroreductive N-debenzylation of structurally diverse N-benzyl compounds was achieved in an undivided cell using a magnesium anode and carbon-felt cathode. Amines, N-heterocycles, amides, carbamates, ureas, lactams, and cyclic ureas were converted to the corresponding N-H products at room temperature without palladium catalysts or H2. The protocol exhibits broad functional-group tolerance and chemoselectively cleaves benzylic C-N bonds while preserving carbonyl frameworks, enabling late-stage deprotection of densely functionalized bioactive-molecule derivatives.

The search for advanced energetic materials has shifted beyond traditional groups like nitro to explore non-conventional explosophores. Among these, the azasydnone ring stands out, combining a zero-oxygen balance with high-energy bonds (N-N, N-O, N=N) for stable energy storage. Here, we report the introduction of azasydnone rings at different positions of dinitropyrazole. Although they have the same substituent group, the change of the position of the azasydone ring makes the two compounds show great differences in crystal density (4-azasydnone-3,5-dinitropyrazole 1.830 g & sdot;cm-3, 5-azasydnone-3,4-dinitropyrazole 1.981 g & sdot;cm-3). Molecular structures are confirmed by 1H and 13C NMR, IR spectroscopy, and X-ray crystal diffraction. This serves as an example of the ability to construction of high-density azasydnone compounds.

Azido energetic compounds are important components of primary explosives because of their excellent initiating ability. However, azido-group installation in energetic molecules usually relies on hazardous reagents such as NaN3. Herein, we report an atom-economical azido-group installation strategy based on an intramolecular Dutt-Wormall-type process that requires neither an external azide reagent nor an additional amine source. Using this approach, azido-containing energetic compound ATPTT was synthesized, showing excellent detonation performance (Dv = 9217 m/s) together with acceptable thermal stability (147 °C) and sensitivity (IS = 3.5 J; FS = 40 N). This work offers a new route to azido-functionalized nitrogen-rich energetic heterocycles and highlights its value for the development of high-performance primary explosives.

Defect engineering has emerged as an effective strategy to enhance the physicochemical properties and catalytic performance of transition metal-based materials. However, its application in combustion catalysts for energetic materials remains insufficiently explored. In this study, high concentrations of oxygen vacancies were introduced into Cu2O via nonmetallic fluorine doping to improve its catalytic performance in the thermal decomposition of ammonium perchlorate (AP) and the energy release of AP/Al formulations. Experimental characterizations and DFT simulations reveal that fluorine doping promotes the formation and thermal stability of oxygen vacancies, which remain abundant at 300 degrees C, enabling strong synergy with Cu active sites. As a result, the 1 wt% F-doped Cu2O catalyst reduced the AP decomposition temperature by 105 degrees C and decreased the activation energy by 103.4 kJ/mol. Furthermore, it significantly enhanced the energetic performance of the AP/Al system, increasing the peak pressure by 461.8 kPa and accelerating the pressurization rate by a factor of 40.6. These findings highlight the promise of defect-engineered metal oxide catalysts for high-efficiency energetic applications.

Organic cathode materials are emerging candidates for aqueous proton batteries due to their structural tunability and sustainability. However, the simultaneous realization of high voltage, low solubility, and high capacity remains a major challenge. In this study, we introduce a biomimetic redox pair, nitroso/hydroxylamine (─N═O ⇌ ─NH─OH), for the first time in energy storage systems. We report 1-(hydroxyamino)anthracene-9,10-dione (NHOH-A), a rationally designed aromatic hydroxylamine compound capable of undergoing a highly reversible proton-coupled two-electron redox process. Benefiting from its strong hydrogen bonding, uniform charge distribution, and extended π-conjugation, NHOH-A delivers a high discharge voltage of 1.15 V, excellent capacity of 224 mAh g −1 , and remarkable cyclability (> 13,000 cycles) when coupled with a Zn anode. Furthermore, leveraging its intrinsic proton-donating capability, we construct a rocking-chair type all-organic proton battery by pairing NHOH-A with an alloxazine anode. The full cell maintains 164 mAh g −1 at 100 C (1 C = 224 mA g −1 ) and delivers an energy density of 125 Wh kg −1 , among the highest for all-organic proton batteries. This work establishes the N═O/NHOH chemistry as a promising redox platform, opening new avenues for developing advanced organic cathodes in energy storage systems.

The bridged-ring strategy was a common approach to enhance the stability and number of modifiable sites for energetic compounds. However, changes in the bridging method can also lead to uncertainty in the energetic performance of the compound, and bridge replacement requires resynthesizing the entire compound. In this work, the carbonyl modifying bridge strategy was confirmed to be an effective method. With the perfection of the carbonyl group, compound bis(3,5-dinitro-1H-pyrazol-4-yl)methanone 4 exhibits high density (ρ = 1.91 g/cm3), excellent thermal stability (Td = 270 °C), good detonation performance (vD = 8579 m/s), and low sensitivity (IS > 40 J), serving as a potential insensitive explosive. Besides, amino functionalized product bis(1-amino-3,5-dinitro-1H-pyrazol-4-yl)methanone 7 significantly alleviated the problem of decreased thermal stability (from 192 °C of 1 to 243 °C of 7). Moreover, the derivative (including ammonium salt and hydroxylamine salt) of compound 4 demonstrates comprehensive performance superiority over that of HL-9, which further validates the efficacy of our strategy. Theoretical and experimental results confirm that introducing conjugation effects to modify the bridge can comprehensively enhance the performance of energetic compounds.

A Brønsted acid‐catalyzed hydroamination of unactivated olefins has been developed, enabling the efficient Markovnikov addition of nitrogen heterocycles to olefins. This reaction utilizes a catalytic amount of trifluoroacetic acid (TFA) to produce a diverse array of N‐alkyl nitrogen heterocycles. The method is highly scalable, allowing for multigram synthesis, and a novel proton transfer species implicated in olefin activation has been identified.

Indole is one of the most prevalent structural frameworks. Notably, C2-substituted indoles bearing an unsubstituted C3-position are recognized as privileged structural motifs in pharmaceutical synthesis. Here, we report a transition-metal-free photocatalytic decarboxylative coupling strategy employing 4CzIPN as the photocatalyst, enabling efficient and dehalogenative C2 functionalization of 3-haloindoles under mild conditions. Moreover, the one-step direct functionalization protocol exhibits excellent scalability, highlighting the synthetic utility of this methodology.

Ultrasmall metal nanoparticles are used as active sites in numerous heterogeneous catalysts. However, the metal sites in these catalysts are typically considered to be static, which limits the transformation of complex organic molecules with special multidimensional spatial structures that are distant from these sites. This study proposes and verifies a swarm mobile catalyst design strategy based on the synergistic induction of the "anchoring-confinement effect". Enhanced catalytic efficiency is achieved by increasing the collision frequency between active sites and reactants. Specifically, the ultrasmall Pd(OH)2 nanoparticles (approximately 1.85 nm), formed under the synergistic effect, are rapidly transformed into mobile Pd species that participate in the reaction. The special support with hierarchical macro-meso-micropores effectively enhances the mass transfer process. The catalyst demonstrates the highest activity in the hydrogenation debenzylation of hexabenzylhexaazaisowurtzitane (HBIW), achieving a high turnover number (TON) of 161.4 and a product yield of 91.4%, with the amount of Pd used in the catalyst being only 0.85 wt parts per thousand of HBIW at near-room temperature. The successful implementation of this strategy offers a new concept for the design and synthesis of efficient heterogeneous catalysts.

Bistetrazoles are highly sought after for developing innovative high-energy density materials. The 1,1'-substituted bistetrazoles, exemplified by TKX-50, have outstanding performance. However, the research of high-perfomance 2,2'-substituted bistetrazoles remains limited. In this work, dinitromethyl groups were introduced into bistetrazole structures as 2,2'-substituted bistetrazoles (BDBTZ), which was extensively characterized through NMR, thermal analysis, and single crystal X-ray diffraction, exhibiting excellent oxygen balance, moderate sensitivity, acceptable thermal stability, high crystal density, and excellent detonation performance.

Herein, we prepared Pd nanoparticle (NP) catalysts using XC-72 carbon supports through a tailored deposition–precipitation method. Our primary objective was to unravel the size effects of Pd NPs on hydrogenation of tetraacetyldibenzylhexaazaisowurtzitane (TADBIW), a pivotal intermediate for synthesis of high energy density materials hexanitrohexaazaisowurtzitane (CL-20). The controlled modulation of Pd NP size ranged from a mere 1.8 nm to 7.4 nm. Remarkably, our investigations into TADBIW hydrogenation unveiled a fascinating trend: the ultrasmall-sized Pd NPs with a diameter of 1.8 nm exhibited excellent yield and reaction rates. In stark contrast, their larger-sized counterparts demonstrated diminished catalytic activities. To disclose the size-dependent nature, various characterization techniques were employed, including XRD, TEM, XPS, CO and H2 pulse chemisorption. The comprehensive analysis revealed that the ultrasmall-sized Pd possessed more positively charged sites and exhibited higher dispersion. This unique configuration facilitated an accelerated adsorption of hydrogen and the electron-rich substrate TADBIW. Notably, this phenomenon led to a reduction in the activation energy through a thermodynamic effect, thereby enhancing overall catalytic performance. Our results strongly suggested that the ultrasmall-sized Pd NPs can exert a dominated influence on the physical and chemical states of the active sites, playing a key role in triggering the adsorption and activation of the substrate TADBIW. These findings not only deepen our understanding of the intricate connections between Pd NP size and catalytic activity but also open new avenues for advancing the design and optimization of catalysts in the hydrodebenzylation methodologies and synthesis of related compounds.

Selective regulation of stability and density via isomerism is a promising strategy for developing energetic materials. In this work, we selectively introduced dinitromethyl groups at different positions of 4-nitro-1,2,3-triazole. The regional heterogeneity endows a high crystal density by virtue of the dense packing; on the other hand, it changes the charge distribution in the molecule, and reinforces the hydrogen bonding interactions, all of which stabilize the material. The resulting compounds exhibit excellent detonation properties and impact sensitivity that are comparable to those of HMX (D-v = 9250 m s(-1) and IS = 10 J).

3,4,5-Trinitropyrazole was successfully functionalized with the trinitromethyl group to give 1-trinitromethyl-3,4,5-trinitropyrazole (3), which was structurally characterized by IR, NMR, elemental analysis, and single -crystal X-ray diffraction. Compound 3 exhibits a super-high density (2.006 g cm(-3) at 170 K, 1.964 g cm(-3) at 296 K), excellent oxygen balance (+18.1 %), and good thermal stability (160 celcius). With X-ray data and quantum computing, the intermolecular interactions of 3 was carefully studied to investigate its structure-property relationship. The high density, excellent oxygen balance, good thermal stability, along with its green feature (chloride free) make compound 3 a potential replacement for ammonium perchlorate (AP) and ammonium dinitramide (ADN) in solid propellants.