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As a typical class of single‐atom catalysts (SACs) possessing prominent advantages of high reactivity, high selectivity, high stability, and maximized atomic utilization, emerging metal‐nitrogen‐doped carbon (M‐N‐C) materials, wherein dispersive metal atoms are coordinated to nitrogen atoms doped in carbon nanomaterials, have presented a high promise to replace the conventional metal or metal oxides‐based catalysts. In this work, recent progress in M‐N‐C‐based materials achieved in both theoretical and experimental investigations is summarized and general principles for novel catalysts design from electronic structure modulating are provided. Firstly, the applications and mechanisms on the advantages and challenges of M‐N‐C‐based materials for a variety of sustainable fuel generation and bioinspired reactions, including the oxygen reduction reaction (ORR), oxygen evolution reaction (OER), hydrogen evolution reaction (HER), carbon dioxide reduction reaction (CO2RR), nitrogen reduction reaction (NRR), and nanozyme reactions are reviewed. Then, strategies toward enhancing the catalytic performance by engineering the nature of metal ion centers, coordinative environment of active centers, carbon support, and their synergistic cooperation, are proposed. Finally, prospects for the rational design of next generation high‐performance M‐N‐C‐based catalysts are outlined. It is expected that this work will provide insights into high‐performance catalysts innovation for sustainable and environmental technologies. The rational design of metal‐nitrogen‐doped carbon (M‐N‐C) materials is at the cutting‐edge of materials research. Herein, the recent progress of M‐N‐C in sustainable fuel generation and biological applications is reviewed. General principles toward designing high‐performance M‐N‐C based nanocatalysts by engineering the nature of metal ion centers, the coordinative environment of active centers, the carbon support, and beyond are outlined.

The term ferroptosis was put forward in 2012 and has been researched exponentially over the past few years. Ferroptosis is an unconventional pattern of iron-dependent programmed cell death, which belongs to a type of necrosis and is distinguished from apoptosis and autophagy. Actuated by iron-dependent phospholipid peroxidation, ferroptosis is modulated by various cellular metabolic and signaling pathways, including amino acid, lipid, iron, and mitochondrial metabolism. Notably, ferroptosis is associated with numerous diseases and plays a double-edged sword role. Particularly, metastasis-prone or highly-mutated tumor cells are sensitive to ferroptosis. Hence, inducing or prohibiting ferroptosis in tumor cells has vastly promising potential in treating drug-resistant cancers. Immunotolerant cancer cells are not sensitive to the traditional cell death pathway such as apoptosis and necroptosis, while ferroptosis plays a crucial role in mediating tumor and immune cells to antagonize immune tolerance, which has broad prospects in the clinical setting. Herein, we summarized the mechanisms and delineated the regulatory network of ferroptosis, emphasized its dual role in mediating immune tolerance, proposed its significant clinical benefits in the tumor immune microenvironment, and ultimately presented some provocative doubts. This review aims to provide practical guidelines and research directions for the clinical practice of ferroptosis in treating immune-resistant tumors.

HighlightsUnique “Janus” interfacial assemble strategy of 2D MXene nanosheets was proposed firstly.Ternary heterostructure consisting of high capacity transitional metal chalcogenide, high conductive 2D MXene and N rich fungal carbonaceous matrix was achieved for larger radius Na/K ions storages.The highly accessible surfaces and interfaces of the strongly coupled 2D based ternary heterostructures provide superb surficial pseudocapacitive storages for both Na and K ions with low energy barriers was verified.Combining with the advantages of two-dimensional (2D) nanomaterials, MXenes have shown great potential in next generation rechargeable batteries. Similar with other 2D materials, MXenes generally suffer severe self-agglomeration, low capacity, and unsatisfied durability, particularly for larger sodium/potassium ions, compromising their practical values. In this work, a novel ternary heterostructure self-assembled from transition metal selenides (MSe, M = Cu, Ni, and Co), MXene nanosheets and N-rich carbonaceous nanoribbons (CNRibs) with ultrafast ion transport properties is designed for sluggish sodium-ion (SIB) and potassium-ion (PIB) batteries. Benefiting from the diverse chemical characteristics, the positively charged MSe anchored onto the electronegative hydroxy (–OH) functionalized MXene surfaces through electrostatic adsorption, while the fungal-derived CNRibs bonded with the other side of MXene through amino bridging and hydrogen bonds. This unique MXene-based heterostructure prevents the restacking of 2D materials, increases the intrinsic conductivity, and most importantly, provides ultrafast interfacial ion transport pathways and extra surficial and interfacial storage sites, and thus, boosts the high-rate storage performances in SIB and PIB applications. Both the quantitatively kinetic analysis and the density functional theory (DFT) calculations revealed that the interfacial ion transport is several orders higher than that of the pristine MXenes, which delivered much enhanced Na+ (536.3 mAh g−1@ 0.1 A g−1) and K+ (305.6 mAh g−1@ 1.0 A g−1 ) storage capabilities and excellent long-term cycling stability. Therefore, this work provides new insights into 2D materials engineering and low-cost, but kinetically sluggish post-Li batteries.

Multimetallic alloys (MMAs) with various compositions enrich the materials library with increasing diversity and have received much attention in catalysis applications. However, precisely shaping MMAs in mesoporous nanostructures and mapping the distributions of multiple elements remain big challenge due to the different reduction kinetics of various metal precursors and the complexity of crystal growth. Here we design a one-pot wet-chemical reduction approach to synthesize core–shell motif PtPdRhRuCu mesoporous nanospheres (PtPdRhRuCu MMNs) using a diblock copolymer as the soft template. The PtPdRhRuCu MMNs feature adjustable compositions and exposed porous structures rich in highly entropic alloy sites. The formation processes of the mesoporous structures and the reduction and growth kinetics of different metal precursors of PtPdRhRuCu MMNs are revealed. The PtPdRhRuCu MMNs exhibit robust electrocatalytic hydrogen evolution reaction (HER) activities and low overpotentials of 10, 13, and 28 mV at a current density of 10 mA cm −2 in alkaline (1.0 M KOH), acidic (0.5 M H 2 SO 4 ), and neutral (1.0 M phosphate buffer solution (PBS)) electrolytes, respectively. The accelerated kinetics of the HER in PtPdRhRuCu MMNs are derived from multiple compositions with synergistic interactions among various metal sites and mesoporous structures with excellent mass/electron transportation characteristics. Nanostructured materials made from multimetal alloys are attractive for catalytic applications. Here, the authors propose a soft-templating approach to prepare mesoporous PtPdRhRuCu nanospheres that feature exposed porous structures rich in highly entropic alloy sites.

HighlightsCatalytically inert 2D Bi2O3 is activated for boosting electrochemical hydrogen evolution reaction (HER) via oxygen vacancy concentration modulation.The relationship between the varied oxygen vacancy concentrations and the corresponding HER activity is revealed by both experimental Vo verification and theoretical density-functional theory calculations.This work provides insights into activating catalytically inert materials into high-performance catalysts.Oxygen vacancies (Vo) in electrocatalysts are closely correlated with the hydrogen evolution reaction (HER) activity. The role of vacancy defects and the effect of their concentration, however, yet remains unclear. Herein, Bi2O3, an unfavorable electrocatalyst for the HER due to a less than ideal hydrogen adsorption Gibbs free energy (ΔGH*), is utilized as a perfect model to explore the function of Vo on HER performance. Through a facile plasma irradiation strategy, Bi2O3 nanosheets with different Vo concentrations are fabricated to evaluate the influence of defects on the HER process. Unexpectedly, while the generated oxygen vacancies contribute to the enhanced HER performance, higher Vo concentrations beyond a saturation value result in a significant drop in HER activity. By tunning the Vo concentration in the Bi2O3 nanosheets via adjusting the treatment time, the Bi2O3 catalyst with an optimized oxygen vacancy concentration and detectable charge carrier concentration of 1.52 × 1024 cm−3 demonstrates enhanced HER performance with an overpotential of 174.2 mV to reach 10 mA cm−2, a Tafel slope of 80 mV dec−1, and an exchange current density of 316 mA cm−2 in an alkaline solution, which approaches the top-tier activity among Bi-based HER electrocatalysts. Density-functional theory calculations confirm the preferred adsorption of H* onto Bi2O3 as a function of oxygen chemical potential (∆μO) and oxygen partial potential (PO2) and reveal that high Vo concentrations result in excessive stability of adsorbed hydrogen and hence the inferior HER activity. This study reveals the oxygen vacancy concentration-HER catalytic activity relationship and provides insights into activating catalytically inert materials into highly efficient electrocatalysts.

Two-dimensional (2D) transition metal oxide systems present exotic electronic properties and high specific surface areas, and also demonstrate promising applications ranging from electronics to energy storage. Yet, in contrast to other types of nanostructures, the question as to whether we could assemble 2D nanomaterials with an atomic thickness from molecules in a general way, which may give them some interesting properties such as those of graphene, still remains unresolved. Herein, we report a generalized and fundamental approach to molecular self-assembly synthesis of ultrathin 2D nanosheets of transition metal oxides by rationally employing lamellar reverse micelles. It is worth emphasizing that the synthesized crystallized ultrathin transition metal oxide nanosheets possess confined thickness, high specific surface area and chemically reactive facets, so that they could have promising applications in nanostructured electronics, photonics, sensors, and energy conversion and storage devices. Two-dimensional metal oxide nanosheets have numerous attractive properties in fields such as photovoltaics and catalysis. Here, the authors show a general approach for the synthesis of these compounds through self-assembly on lamellar reverse micelles.

Single‐atomic transition metal–nitrogen–carbon (M–N–C) structures are promising alternatives toward noble‐metal‐based catalysts for oxygen reduction reaction (ORR) catalysis involved in sustainable energy devices. The symmetrical electronic density distribution of the M─N 4 moieties, however, leads to unfavorable intermediate adsorption and sluggish kinetics. Herein, a Fe–N–C catalyst with electronic asymmetry induced by one nearest carbon vacancy adjacent to Fe─N 4 is conceptually produced, which induces an optimized d‐band center, lowered free energy barrier, and thus superior ORR activity with a half‐wave potential ( E 1/2 ) of 0.934 V in a challenging acidic solution and 0.901 V in an alkaline solution. When assembled as the cathode of a Zinc–air battery (ZAB), a peak power density of 218 mW cm −2 and long‐term durability up to 200 h are recorded, 1.5 times higher than the noble metal‐based Pt/C+RuO 2 catalyst. This work provides a new strategy on developing efficient M–N–C catalysts and offers an opportunity for the real‐world application of fuel cells and metal–air batteries.

•EEG-based multi-scale deep learning predicts individual iTBS response in major depressive disorder.•Two neurophysiological subtypes are identified with distinct baseline symptoms and clinical outcomes.•DCM-PEB analysis reveals subtype-specific frontal–temporal–parietal–motor connectivity patterns.•Connectivity patterns correlate with treatment efficacy, suggesting candidate mechanistic biomarkers. Response to transcranial magnetic stimulation (TMS) in major depressive disorder (MDD) is highly variable, underscoring the need for biomarkers that both predict treatment efficacy and elucidate underlying neural mechanisms. We integrated deep learning and computational modeling to identify subtype-specific responses to intermittent theta-burst stimulation (iTBS) in MDD. Resting-state EEG and event-related potentials were collected from 198 patients across two independent cohorts (training: N = 125; validation: N = 73). A total of 55,476 EEG epochs were analyzed using a multi-scale convolutional recurrent neural network (MCRNN). To probe circuit-level mechanisms, Dynamic Causal Modeling with Parametric Empirical Bayes (DCM-PEB) was applied to assess subtype-specific effective connectivity. The MCRNN achieved robust predictive performance (accuracy = 0.91; 95% CI: 0.85–0.97 in the training cohort; 0.86; 95% CI: 0.76–0.96in the validation cohort), reliably stratifying patients into two neurophysiological subtypes. These subtypes differed in baseline symptom severity and clinical response trajectories. DCM-PEB revealed distinct effective connectivity signatures within frontal–temporal–parietal–motor circuits, with posterior probability exceeding 0.99, linking subtype-specific neural dynamics to treatment outcomes. EEG-based deep learning, combined with biophysically informed connectivity modeling, enables reliable prediction of iTBS outcomes in MDD. Subtype-specific disruptions in frontal–temporal coupling emerge as candidate biomarkers, offering mechanistic insight into neuromodulation response and a framework for personalized TMS interventions.

The development of highly efficient and stable oxygen reduction electrocatalysts and revealing their underlying catalytic mechanism are crucial in expanding the applications of metal‐air batteries. Herein, an excellent FeCo alloy nanoparticles (NPs)‐decorated N‐doped mesoporous carbon electrocatalyst (FeCo/NC) for oxygen reduction reaction, prepared through the pyrolysis of a dual metal containing metal‐organic framework composite scaffold is reported. Benefiting from the highly exposed bimetal active sites and the carefully designed structure, the Fe0.25Co0.75/NC‐800 catalyst exhibits a promising electrocatalytic activity and a superior durability, better than those of the state‐of‐the‐art catalysts. Suggested by both the X‐ray absorption fine structures and the density functional theoretical calculation, the outstanding catalytic performance is originated from the synergistic effects of the bimetallic loading in NC catalysts, where the electronic modulation of the Co active sites from the nearby Fe species leads to an optimized binding strength for reaction intermediates. This work demonstrates a class of highly active nonprecious metals electrocatalysts and provides valuable insights into investigating the structure–performance relationship of transition metal‐based alloy catalysts. A FeCo alloy nanoparticles (NPs)‐functionalized N‐doped mesoporous carbon material is constructed and demonstrated as a promising catalyst for oxygen reduction reaction. Through modulating the electronic structure of FeCo NPs in the framework, a moderate binding energy for oxygen intermediate species is generated, thus boosting the catalytic performance.

Exploring low‐cost and high‐efficient electrocatalyst is an exigent task in developing novel sustainable energy conversion systems, such as fuel cells and electrocatalytic fuel generations. 2D materials, specifically 2D superlattice materials focused here, featured highly accessible active areas, high density of active sites, and high compatibility with property‐complementary materials to form heterostructures with desired synergetic effects, have demonstrated to be promising electrocatalysts for boosting the performance of sustainable energy conversion and storage devices. Nevertheless, the reaction kinetics, and in particular, the functional mechanisms of the 2D superlattice‐based catalysts yet remain ambiguous. In this review, based on the recent progress of 2D superlattice materials in electrocatalysis applications, the rational design and fabrication of 2D superlattices are first summarized and the application of 2D superlattices in electrocatalysis is then specifically discussed. Finally, perspectives on the current challenges and the strategies for the future design of 2D superlattice materials are outlined. This review attempts to establish an intrinsic correlation between the 2D superlattice heterostructures and the catalytic properties, so as to provide some insights into developing high‐performance electrocatalysts for next‐generation sustainable energy conversion and storage. 2D superlattice materials combining the advantages of 2D materials and advanced composites provide tunable physical and chemical properties to meet diverse requirements in different applications. This review article summarizes the major fabrication methods for preparing 2D superlattice materials and reviews their applications in electrocatalysis involved in emerging energy devices.