Sustainable solar-induced decontamination of waterborne pharmaceutical pollutants using a structurally engineered Ti3C2 MXene/Bi2MoO6/g-C3N4 S-scheme heterocatalyst with tri-component interfacial charge transfer.

Efficient oxygen reduction reaction (ORR) catalysts are pivotal for advancing clean energy technologies, such as fuel cells and metal-air batteries. Metalloporphyrins and metallocorroles, inspired by biological systems, represent promising molecular catalysts for the ORR due to their tunable structures and redox properties. This review systematically explores recent progress made in developing metalloporphyrin- and metallocorrole-based catalysts for the ORR, spanning from fundamental molecular design to advanced material engineering. We first introduce the fundamentals of the ORR and its significance. The discussion then delves into molecular catalysis, covering both homogeneous and heterogeneous catalytic systems. For heterogeneous systems, in addition to directly loading molecular catalysts on electrode materials through physical adsorption, we discuss covalent grafting of molecular catalysts on carbon supports (e.g., carbon nanotubes, graphene, and carbon black) and other support materials (e.g., metal oxides and gold electrodes). Moreover, the other focus of this review is placed on elucidating structure-property relationships, particularly on analyzing the effect of substituents, trans axial ligands, proton relay groups, electrostatic effects, and binuclear structures on the ORR mechanism and performance. Furthermore, the integration of these molecular catalysts into structured porous materials, including metal-organic frameworks (MOFs), covalent-organic frameworks (COFs), and porous organic polymers (POPs), is discussed, highlighting how material design enhances catalytic activity, stability, and electron/proton transport. Finally, this review summarizes key achievements, identifies current challenges, and offers perspectives on future research directions for developing next-generation, high-performance ORR catalysts based on metalloporphyrins and metallocorroles. This work aims to provide valuable insights for the rational design of efficient and durable metalloporphyrin- and metallocorrole-based ORR catalysts and for the development of molecule-based functional materials for the future application of molecular electrocatalysis.

The oxygen reduction reaction is significantly important for metal-air batteries, yet the sluggish reaction kinetics limited by slow proton-coupled electron transfer has hindered their further application. Here, dual Cr and Fe atoms are incorporated into a high-curvature carbon nano-onion (Onion-CrFeDSA) to demonstrate significantly synergistic regulation of proton generation and transfer from the dual catalytic centers. The electrochemical measurements confirmed that the dual-site configuration in Onion-CrFeDSA could enhance the ORR performance with a half-wave potential of 0.916 V and a kinetic current density of 26.45 mA cm-2. Besides, a high turnover frequency (TOF) of 7.44 s-1 together with a high mass activity of 51.42 A mgFe-1 are also achieved for the as-obtained dual atomic catalysts. A series of operando techniques, combined with density functional theory calculations, revealed that Cr atoms mainly contribute to water dissociation and proton transfer, while Fe atoms predominantly catalyze oxygen reduction and intermediate conversion. Moreover, the Onion-CrFeDSA-assembled aqueous and quasi-solid zinc-air batteries achieve impressively high maximum power densities of 314.7 mW cm-2 and 163.3 mW cm-2, representing a top-tier Fe-based ORR catalyst. This work proposes a feasible way to enhance the ORR performance by engineering adjacent catalytic centers to cooperatively mediate the proton-coupled electron transfer.

Wildfires drastically alter biogeochemical cycling and transport of nutrient elements, including nitrogen (N), from terrestrial to aquatic ecosystems, with the potential to degrade water quality. Understanding the impact of characteristics of wildfire-derived ashes and burned soils on the mobilization of N is essential for effectively managing wildfires and mitigating adverse effects on watershed functions. This study quantified the mobility of N in soils and ashes influenced by wildfires in the northern California/Nevada region in the western United States (Dixie, Beckwourth, and Caldor fires) and the impact of soil/ash characteristics. The mobile fraction of N ranged from 0.025-0.070 for the ashes, and the mobile fraction of N was composed of 13.1-39.6% as NO3-, up to 0.011% as NO2-, 0.004-86.9% as NH3/NH4+, and up to 49.4% as dissolved organic N. The speciation indicates possible nitrification occurring during the wildfires, but suggests no substantial denitrification. The mobile fraction of N was 11.3 ± 7.4 times that of organic carbon (OC), due to the high mobility of inorganic N (mainly NO3- and NH3/NH4+) and nitrogenous organic compounds. The mobile N fraction was associated with redox reactions of iron during wildfires, and was regulated by the redox reactivity of OC. N mobility in the ashes was lower than in control soils, potentially due to the transformation in the speciation of N. However, the total amount of mobile N was increased by wildfire, with the amount of increase being closely related to the severity of wildfires. Overall, wildfires lead to more mobile N, including both organic and inorganic N regulated by redox reactions and severity of wildfires, with subsequent concerns for water quality and water/wastewater treatment processes.

This work presents the synthesis of a molecular crystal of adiponitrile (Adpn) and LiI via a simple melting method. The molecular crystal has both Li+ and I- channels and can be either a Li+ or an I- conductor. In the stoichiometric crystal (Adpn)2LiI, the Li+ ions interact only with four CN groups of Adpn, while the I- ions are uncoordinated. Ab initio calculations indicate that the activation energy for ion hopping is less for the I- ions (Ea = 60 kJ mol-1) than that for the Li+ ions (Ea = 93 kJ mol-1), and this crystal is predominantly an I- conductor, with a lithium-ion transference number (tLi+) of tLi+ = 0.15; no lithium plating/stripping is observed in the cyclic voltammograms (CVs), with a conductivity of σ = 10-4 S cm-1 at 30 °C. With the addition of excess adiponitrile, which resides in the grain boundaries between the crystal grains, the contribution of Li+ ions to the conductivity increases, so that for the nonstoichiometric molecular crystal (Adpn)3LiI, Li ↔ Li+ redox reactions are observed in the CVs, tLi+ = 0.63, conductivity increases to σ = 10-3 S cm-1 at 30 °C, and the voltage stability window is 4 V, and it is thermally stable up to 130 °C, showcasing the potential of this electrolyte for advanced solid-state Li-I battery applications. The solid (Adpn)3LiI electrolyte minimizes the migration of polyiodides, inhibiting the "shuttle" effect.

Nanolaminates─atomically layered stacks of dissimilar oxides─are widely used to engineer dielectric behavior at the nanometer scale. Among these, atomic layer deposition (ALD)-grown Al2O3/TiO2 stacks have been reported to exhibit "giant" dielectric constant (κ ∼ 103) at subnanometer periods. Here we show that the apparent high-κ is not an intrinsic dielectric enhancement but a measurement artifact arising from electrically percolative Al2O3/TiO2 stacks treated as ideal dielectrics. Using Al2O3/TiO2 nanolaminate metal-insulator-metal (MIM) capacitors and a combination of electrical (C-f, I-V, EIS), spectroscopic (XPS, HAXPES), and structural (TEM) measurements, we found that TMA/H2O growth yields Al-deficient Al2O3 on TiO2 that appears morphologically continuous yet lacks full atomic closure, forming electronically percolative pathways that recover insulating behavior only after a fully coalesced overlayer develops. In contrast, TMA/O3 deposition produces fully continuous Al2O3 that remains insulating even at subnanometer thickness. These results establish practical design rules, showing that oxidant chemistry and film thickness together govern film continuity and insulating behavior, thereby clarifying when ultrathin ALD Al2O3 functions as a true insulator versus a quasi-conductive layer. The insights extend directly to applications in microelectronics (gate stacks, MIM/DRAM capacitors), quantum devices (2DEGs, tunnel barriers), and electrochemical/photovoltaic systems (battery electrodes, electrocatalysts, and perovskite interface engineering), where reliable subnanometer coatings are essential.

ABSTRACT V‐based materials, with the high specific capacity and multi‐electron redox reactions, are considered as preferred cathodes for low‐cost and high‐safety aqueous zinc‐ion batteries. Nevertheless, poor electronic conductivity, sluggish kinetics, vanadium dissolution, and unstable structure pose severe challenges for the further practical applications. To address these issues, in this study, transition metal ions Mo 6+ and polyaniline were incorporated into V 2 O 5 derived from vanadium acetylacetonate via a one‐step hydrothermal method (MPVO). The results reveal that MPVO exhibits a unique three‐dimensional (3D) sea urchin‐like morphology with a satisfactory specific surface area and high concentration of oxygen vacancies. These characteristics offer more reaction sites for Zn 2+ and adjust the electronic conductivity. Moreover, kinetic analysis and density‐functional‐theory calculations indicate that MPVO performs metallic behavior, with the lowest Zn 2+ diffusion barrier and outstanding pseudocapacitive storage capacity. Hence, the MPVO cathode delivers a reversible capacity of approximately 457.5 mAh g −1 at 0.1 A g −1 . Moreover, it demonstrates remarkable high‐rate capacity and robust long‐cycle performance. This study realizes a triple‐strategy approach of enlarging the interlayer spacing, evolving from a zero‐dimensional (0D) to 3D sea urchin‐like morphology, and introducing abundant defects. These synergistic strategies significantly enhance the rapid kinetics and high stability of the MPVO cathode and provide new insights for designing V‐based cathodes.

Orthoester-containing natural products possess unique oxygen-rich architectures; however, the enzymatic mechanism responsible for constructing these functional groups has remained unclear. In this study, we report the structure-function analysis of NvfE, a nonheme iron enzyme from Aspergillus novofumigatus, which catalyzes the Fe(II)-dependent isomerization of a reactive endoperoxide to generate the orthoester fumigatonoid C. Structural analysis of NvfE revealed that, although structurally similar to Fe(II)/αKG-dependent oxygenases, NvfE lacks the canonical αKG-binding pocket and instead features a nonconserved Glu149 residue that governs substrate recognition. Site-directed mutagenesis and QM/MM calculations confirmed the critical role of Glu149 in catalysis. Notably, Glu149 variants produced an alternative orthoester isomer, indicating its importance for product selectivity. Based on these results, we propose a mechanism for the unique αKG-free NvfE-catalyzed orthoester formation reaction. These results unveil a remarkable catalytic strategy for orthoester biogenesis and demonstrate the functional diversification of nonheme iron enzymes beyond oxidative chemistry.

ABSTRACT Iron‐based Prussian blue analogs (PBAs) represent promising, facile‐to‐prepare, and low‐cost positive electrode materials for sodium‐ion batteries. However, their practical application is hindered by the markedly irreversible three‐phase transitions and severe lattice distortion that occur during sodium ion storage, leading to capacity limitations and diminished cycling stability. Herein, a simple pyrrole‐induced phase transition engineering strategy is proposed to successfully transform monoclinic PBAs into cubic polypyrrole‐PBAs (PPy‐PBAs). In situ X‐ray diffraction (XRD) testing and density functional theory (DFT) calculations reveal that the phase transition mechanism transforms from an unfavorable three‐phase process to a highly reversible two‐phase transition. Compared to complex three‐phase transition (PBAs), the efficient two‐phase transition (PPy‐PBAs) exhibits smaller lattice volume contraction/expansion and less Fe‐C/Fe‐N bond length stretching/shrinking, demonstrating remarkable structural stability. Moreover, this strategy effectively reduced the energy barrier for sodium‐ion (Na + ) migration, with the density of states crossing the Fermi level, significantly enhancing electronic conductivity, and thereby facilitating redox reactions and Na + transport kinetics within the material. The reversible two‐phase transition enables sustainable sodium‐ion storage through phase‐transition engineering. Compared with PBAs that undergo structural distortion and significant lattice strain, the optimized positive electrode material demonstrates a discharge capacity of 136 mAh/g and an ultralong stable cycling lifespan of 1700 cycles, establishing new possibilities for advanced sodium‐ion batteries.

Amidst depleting traditional energy resources and pressing demands for sustainable technologies, developing efficient, low-cost and pH-universal oxygen reduction reaction (ORR) catalysts is crucial for advancing fuel cells and metal-air battery. Currently, Pt-based materials represent the most efficient electrocatalysts for ORR, yet their commercial deployment is constrained by high costs and moderate stability. In this work, we successfully encapsulated SnSb alloy nanoparticles in N-doped porous carbon using 4,5-dicyano-2-aminoimidazole as a dual-functional molecular precursor with sacrificial MgO templates, achieving nanolevel metal dispersion and alloy-carbon coupling. The catalyst, incorporating N-doped porous carbon with a high specific surface area and nanosized SnSb alloy as active sites, exhibits outstanding ORR activity with half-wave potentials (E1/2) of 0.87 V in 0.1 M KOH, 0.76 V in 0.1 M PBS, and 0.67 V in 0.5 M H2SO4, which DFT calculations attribute to favorable d-band modulation and optimized intermediate adsorption from Sn-Sb synergy. In zinc-air battery, the catalyst delivers a peak power density of 169 mW·cm-2 and an energy density of 848.8 Wh·kgZn-1 at 10 mA·cm-2, markedly higher than Pt/C benchmarks, confirming its significant potential for practical energy-conversion devices.

Herein, we present a theoretical framework to uncover the crucial roles of interlayer magnetic exchange of two-dimensional hexaaminobenzene (HAB)-based metal-organic frameworks (TM-HAB) catalysts on electrocatalytic oxygen reduction reaction (ORR) performance. Through multistage screening, monolayer Fe-HAB-I and Co-HAB-I were identified as optimal for 4e- and 2e- ORR pathways, respectively. Grand Canonical Density Functional Theory (GC-DFT) and Monte Carlo simulations revealed monolayer Co-HAB-I prefers to a 2e- ORR with an onset potential of 0.95 V vs RHE under alkaline conditions, while Fe-HAB-I exhibits 4e- ORR activity at the onset potential of 0.73 V vs RHE in acidic environments. For experimentally relevant multilayer systems, GC-DFT calculation of bilayer Fe-HAB-II highlights the critical role of interlayer magnetic coupling: the ferromagnetic (FMII) state demonstrates a markedly higher onset potential than the antiferromagnetic (AFMII) state at pH = 13. Notably, Fe-HAB-II in the FMII state achieves a theoretical onset potential of 1.17 V vs RHE, closely aligning with experimental observations (1.02 V vs RHE), thereby validating the crucial roles of interlayer spin exchange on ORR property. This work underscores the pivotal influence of interlayer magnetic interactions in optimizing two-dimensional electrocatalysts for ORR.

The widespread application of Pt-based catalysts in fuel cells is limited by their high cost and insufficient durability for both the oxygen reduction reaction (ORR) and alcohol oxidation reactions (AOR). Herein, we designed a bifunctional catalyst featuring Pt nanoparticles anchored on the nitrogen-doped carbon support engineered with atomically dispersed Fe-N4 and Co-N4 dual sites (Pt/FeCoNC) for efficient ORR and AOR. For the acidic ORR, Pt/FeCoNC delivers a half-wave potential of 0.90 V vs RHE, with mass and specific activities 5.6 and 5.1 times higher than commercial Pt/C. Impressively, it retains nearly 60% of its initial mass activity after 30,000 durability cycles, far exceeding Pt/C (∼33% retention). Furthermore, the prepared catalyst demonstrates exceptional AOR activity, with mass activities for methanol and ethanol oxidation over 3 times greater than Pt/C. The prepared catalyst utilizes a strong synergistic interaction between Pt and the bimetallic sites to induce electron delocalization, which downshifts the Pt d-band center. This electronic modulation simultaneously weakens the adsorption of poisoning intermediates and enhances nanoparticle stability. The results establish dual-atom site engineering as a highly effective approach to design durable and active bifunctional catalysts for energy conversion.

Memristors based on 2D materials are promising for compact and energy-efficient neuromorphic hardware. However, conventional devices require paired elements to implement bidirectional weight updates, such as spike-timing-dependent plasticity (STDP) and anti-STDP for supervised spiking neural networks (SNN) such as the remote supervised method. Here, an Au/Ti/2D Sr2Nb3O10 perovskite-oxide nanosheet (SNO PON)/Pt memristor is demonstrated that exhibits dual bipolar resistive switching, supporting clockwise (interface) and counter-clockwise (filament) switching. Ultrathin (≈5nm) SNO PONs, fabricated over wafer-scale areas by Langmuir-Blodgett deposition, serve as dynamic reservoirs for oxygen ions and vacancies. Voltage-induced redox reactions at the Ti electrode are accompanied by the formation of oxygen vacancies in the SNO, as confirmed through cross-sectional transmission electron microscopy and electron energy-loss spectroscopy. The memristor exhibits stable resistance states with >103s retention and <0.2V set variation across 30 cells. Bidirectional plasticity under dual-polarity pulse trains replicates STDP/anti-STDP rules, enabling a 3×3 array to encode pixel patterns with opposite-polarity pulses. A leaky integrate-and-fire SNN model achieves 86.4% accuracy on the MNIST dataset using identical pre- and post-synaptic spike waveforms. These findings establish dual bipolar 2D memristors as scalable and efficient components for high-density, simplified supervised SNN hardware.

The development of efficient and sustainable heterogeneous catalysts remains central to the advancement of green oxidation chemistry. Herein, we report a Ni-salphen-derived metalated porous organic polymer (Ni@CAB), synthesized via a simple Friedel-Crafts alkylation strategy that integrates atomically dispersed Ni-N2O2 active sites into a robust carbazole-linked framework. A combination of 2D solid-state 13C-1H double cross-polarization (CP) correlation NMR, XPS, synchrotron-based XAS, and electron microscopy techniques confirmed the structural integrity, amorphous porous architecture, and uniform dispersion of Ni centers. Electronic analyses revealed reduced surface electron density at the Ni sites, enhancing their Lewis acidity and catalytic reactivity. Ni@CAB demonstrated exceptional performance in the aerobic allylic oxidation of cyclohexene under ambient conditions, affording complete conversion with high selectivity and remarkable recyclability over multiple cycles without detectable Ni leaching. Complementary DFT calculations unveiled favorable charge transfer and energetically viable pathways consistent with experimental observations. This study establishes surface electron density as a powerful activity descriptor and underscores the promise of rationally engineered metalated porous polymers for sustainable oxidation catalysis.

Abstract Overcoming the intrinsic activity‐selectivity contradiction to achieve simultaneously high electrocatalytic activity and near‐unity four‐electron (4e − ) selectivity in the oxygen reduction reaction (ORR) is critical for advancing the efficiency of metal‐air batteries. Transition metal catalysts exhibit divergent ORR behaviors governed by distinct π * d‐orbital occupancies, a phenomenon known as the “oxo‐wall” effect, which dictates the stability of critical terminal metal oxo/oxyl intermediates. The synergistic integration of pre‐ and post‐oxo‐wall metal sites offers a promising strategy to overcome the limitation, while there is a lack of relevant research and understanding of the dual‐site cooperation. Herein, the design and synthesis of a covalently immobilized Co/Fe‐porphyrin catalyst are reported to validate a dual‐site cascade mechanism: O 2 undergoes initial two‐electron (2e − ) reduction at post‐oxo‐wall Co sites exhibiting high activity but low 4e − selectivity, followed by sequential H 2 O 2 reduction to H 2 O at pre‐oxo‐wall Fe sites with high 4e − selectivity. Spatial isolation enforced by porphyrin ligands and covalent grafting prevents inter‐sites interference. This architecture successfully circumvents the activity‐selectivity contradiction, delivering enhanced ORR performance with a half‐wave potential of 0.79 V vs RHE alongside high 4e − selectivity. The work provides molecular‐level insights into decoupling activity‐selectivity trade‐offs, establishing a dual‐site design paradigm for energy conversion electrocatalysts.

The unique advantages of single-atom catalysts (SACs), including exceptional atom utilization efficiency, distinctive quantum confinement effects, and precisely modifiable electronic configurations, have established them as a leading frontier in electrocatalysis research. These properties make SACs promising candidates for the oxygen reduction reaction (ORR). Nevertheless, the present research predominantly concentrates on single-pH environments, with scarce reports addressing the development of dual-environment catalysts capable of maintaining high performance across both acidic and alkaline conditions. In this investigation, a highly dispersed iron single-atom catalyst (FeSA) was synthesized via a facile pyrolysis strategy using a zeolitic imidazolate framework-8 (ZIF-8) precursor and dopamine as the nitrogen/carbon source. The resultant FeSA demonstrated remarkable ORR catalytic performance, exhibiting half-wave potentials (E1/2) of 0.85 V (vs RHE in 0.5 M H2SO4) and 0.88 V (vs RHE in 0.1 M KOH), respectively. When implemented in zinc-air battery (ZAB) systems, the catalyst exhibited a superior electrochemical performance, achieving a specific capacity of 790 mAh gZn-1 and a peak power density of 221 mW cm-2. These findings highlight the catalyst's potential for useful applications in systems for converting and storing renewable energy. The dual-environment catalytic capability of this FeSA material represents a significant advancement for single-atom electrocatalysis, addressing a critical gap in current catalyst design paradigms.

The reproducibility of oxygen reduction reaction (ORR) activity assessment for platinum-based electrocatalysts using the rotating disk electrode (RDE) method is critically dependent on the quality of the fabricated catalytic layer. This work presents a comprehensive study on optimizing catalytic ink formulation—specifically the water-to-isopropanol (H2O:IPA) solvent ratio and the ionomer-to-carbon (I/C) ratio—to achieve a homogeneous catalytic layer and ensure high data reproducibility for monometallic Pt/C and bimetallic PtCu/C catalysts. A key aspect of this research is the implementation of a simple and effective visual inspection method using a benchtop digital microscope to rapidly assess catalytic layer quality, which was shown to correlate directly with electrochemical performance. The optimal ink composition was found to be catalyst-specific. For Pt/C, the highest mass activity of 353 A/g~Pt~ was achieved with a solvent ratio of 1:3 (H2O:IPA) and an I/C ratio of 0.3. For PtCu/C, the best performance was obtained with the same solvent ratio (1:3) but a higher I/C ratio of 0.4, yielding a mass activity of 491 A/g~Pt~. It was demonstrated that ink compositions leading to layer inhomogeneities, such as aggregates and “coffee-ring” effects, significantly impair mass transport and lead to underestimated ORR activity. The study underscores the absence of a universal ink recipe and establishes that the optimization of ink parameters for each specific catalyst is essential for obtaining reliable and reproducible electrochemical data.

To enhance chemodynamic therapy (CDT) and induce calcium overload in tumor cells, we developed a novel nanocatalyst, Cu/ZIF-8@CaS2O3@PEG (CZCaP) via a dual-pathway strategy. The system was constructed based on a biocompatible ZIF-8 scaffold, which incorporated Cu2+ ions as the catalytic center and was loaded with calcium thiosulfate (CaS2O3) as a therapeutic agent. The surface of the nanocatalyst was modified with PEG to enable a tumor microenvironment (TME)-responsive drug release. Under acidic TME conditions, CZCaP dissociated to release CaS2O3 and Cu2+. The thiosulfate ions (S2O32-) acted as a cocatalyst by donating electrons to hydroperoxyl (•OOH) radicals generated from H2O2 decomposition. This reaction accelerated the Cu(II)/Cu(I) redox cycling, leading to an enhanced production of hydroxyl radicals (•OH). Consequently, glutathione (GSH) was depleted, compromising the antioxidant capacity of tumor cells. Simultaneously, •OH-mediated oxidative damage impaired PMCA4, a calcium efflux pump, resulting in intracellular accumulation of Ca2+ and ultimately calcium overload. Furthermore, •OH downregulated the antiapoptotic protein Bcl-2, collapsed the mitochondrial membrane potential, and promoted calcium influx into mitochondria, thereby inducing apoptosis. By integrating inorganic cocatalysis with the disruption of calcium signaling, this system overcomes the limitation of conventional CDT and presents an innovative multimodal strategy for tumor therapy.

CPT1 (carnitine palmitoyl transferase 1) is a rate-limiting enzyme for long-chain fatty acid oxidation. In adult hearts, CPT1b predominates, while CPT1a is coexpressed at lower levels. Pathological stress on the heart induces CPT1a expression, coinciding with a reduction in fatty acid oxidation, yet the role of CPT1a in pathological remodeling is unknown. CPT1 isoform expression was assayed in the myocardium of patients with heart failure with nonischemic cardiomyopathy and a preclinical mouse model of heart failure. Mice were subjected to afterload stress via transverse aortic constriction (TAC) or sham surgery (sham) with cardiac-specific CPT1a knockdown or cardiac-specific, adeno-associated virus serotype 9-mediated CPT1a overexpression (adeno-associated virus serotype 9.cTNT [cardiac troponin T].Cpt1a) versus empty virus or PBS infusions as controls. MicroRNA 370, known to suppress hepatic CPT1a, was assayed and overexpressed to determine if microRNA 370 regulates cardiac CPT1a expression. CPT1a protein was elevated and microRNA 370 reduced in the myocardium of male and female patients with nonischemic cardiomyopathy, as well as in failing mouse hearts. Adeno-associated virus-mediated microRNA 370 overexpression in mouse hearts suppressed CPT1a expression and attenuated the response of CPT1a to TAC. Preventing CPT1a upregulation in response to TAC in cardiac-specific CPT1a knockout mice exacerbated adverse remodeling, severe dysfunction, and increased mortality. In contrast, CPT1a overexpression (2.8-fold) attenuated impaired ejection fraction (by 54%) versus control TAC hearts (P<0.05). Delivery of adeno-associated virus serotype 9.cTnT.Cpt1a 4 weeks after TAC surgery led to significant rescue of ejection fraction and mitigated the exacerbated dysfunction of cardiac-specific CPT1a knockout mice TAC hearts. RNA-seq revealed a novel function of CPT1a in suppressing hypertrophic, profibrotic, and cell death gene programs in both sham and TAC hearts, irrespective of changes in fatty acid oxidation, with reduced histone acetylation. The effects of CPT1a in the heart extend beyond fatty acid oxidation including noncanonical regulation of gene programs. CPT1a upregulation occurs in nonischemic cardiomyopathy and is a critical cardioprotective adaptation to pathological stress.

Electrochemical two-electron oxygen reduction reaction (2e– ORR) in neutral environments holds remarkable promise for sustainable hydrogen peroxide (H2O2) production. However, its practical application is largely hindered due to the scarcity of electrocatalysts with high selectivity and durability under ampere-level current densities. Herein, a hydrogen-bonded organic framework@conductive metal-organic framework (HOF@cMOF) heterostructure is designed for industrial-level H2O2 electrosynthesis. Through integrating DAT-HOF (DAT=diaminotriazole) and Co-cMOF, Co-N bonds formed at the heterointerface modulates the electronic structure of Co sites, optimizing the adsorption strength of oxygen intermediates with improved activity and selectivity. Besides, the formation of built-in electric field drives the proton migration from DAT-HOF to Co-cMOF, facilitating the O2 protonation to H2O2 at Co sites. In further combination with the high proton donation capability of DAT-HOF and high conductivity of Co-cMOF, efficient H2O2 production is achieved with a H2O2 Faradic efficiency of 97.1 ± 0.4%, a H2O2 yield of 738.9 mg h⁻1 cm⁻2 and a long-term durability over 100 h at 1200 mA cm⁻2. This work offers a high-performance electrocatalyst for promoting the industrial implementation of H2O2 electrosynthesis.