Abstract Elucidating the synergistic catalytic mechanism between multiple active centers is of great significance for heterogeneous catalysis; however, finding the corresponding experimental evidence remains challenging owing to the complexity of catalyst structures and interface environment. Here we construct an asymmetric TeN 2 –CuN 3 double-atomic site catalyst, which is analyzed via full-range synchrotron pair distribution function. In electrochemical CO 2 reduction, the catalyst features a synergistic mechanism with the double-atomic site activating two key molecules: operando spectroscopy confirms that the Te center activates CO 2 , and the Cu center helps to dissociate H 2 O. The experimental and theoretical results reveal that the TeN 2 –CuN 3 could cooperatively lower the energy barriers for the rate-determining step, promoting proton transfer kinetics. Therefore, the TeN 2 –CuN 3 displays a broad potential range with high CO selectivity, improved kinetics and good stability. This work presents synthesis and characterization strategies for double-atomic site catalysts, and experimentally unveils the underpinning mechanism of synergistic catalysis.

Metal ion substitution and anion exchange are two effective strategies for regulating the electronic and geometric structure of spinel. However, the optimal location of foreign metallic cations and the exact role of these metals and anions remain elusive. Herein, CoFe2O4-based hollow nanospheres with outstanding oxygen evolution reaction activity are prepared by Cr3+ substitution and S2– exchange. X-ray absorption spectra and theoretical calculations reveal that Cr3+ can be precisely doped into octahedral (Oh) Fe sites and simultaneously induce Co vacancy, which can activate adjacent tetrahedral (Td) Fe3+. Furthermore, S2– exchange results in structure distortion of Td-Fe due to compressive strain effect. The change in the local geometry of Td-Fe causes the *OOH intermediate to deviate from the y-axis plane, thus enhancing the adsorption of the *OOH. The Co vacancy and S2– exchange can adjust the geometric and electronic structure of Td-Fe, thus activating the inert Td-Fe and improving the electrochemical performance.

Abstract The fabrication of heterostructures has inspired extensive interest in promoting the performance of solar cells or solar fuel production, but it is still challenging for nitrides to prepare structurally ordered heterostructures. Herein, one nickel nitride‐based heterostructure composed of 1D Ni 0.2 Mo 0.8 N nanorods and 0D Ni 3 N nanoparticles (denoted as NiMoN/NiN) is reported to exhibit significantly promoted hydrogen evolution reaction performance in both alkaline and neutral media. In particular, the optimal overpotential of the NiMoN/NiN sample at 10 mA cm −2 in 1 m KOH is 49 mV. The successful fabrication of 1D/0D heterostructures is mainly ascribed to morphology‐inherited nitridation of 1D oxide precursor (denoted as NiMoO‐NRs) in situ grown on Ni foam surface, and attributed to strong Lewis acid–base interaction that renders the Ni 2+ ions emitted from the oxide precursor to well coordinate with NH 3 for the formation of Ni 3 N nanoparticles during the nitridation process. It is theoretically and experimentally demonstrated that the special 1D/0D heterostructure provides tandem active phases Ni 0.2 Mo 0.8 N and Ni 3 N for synergistic promotion in lowering the activation energy of H 2 O dissociation and optimizing the adsorption energy of H, respectively. This work may open a new avenue for developing highly active tandem electrocatalysts for promising renewable energy conversion.

Highly efficient La/Sr-based perovskites with surface Fe sites and Sr vacancies were developed for the active lattice oxygen mechanism (LOM) of the oxygen evolution reaction (OER), and a relationship between the LOM and dynamic surface structure was established.

Abstract Complex metal nanoparticles distributed uniformly on supports demonstrate distinctive physicochemical properties and thus attract a wide attention for applications. The commonly used wet chemistry methods display limitations to achieve the nanoparticle structure design and uniform dispersion simultaneously. Solid-phase synthesis serves as an interesting strategy which can achieve the fabrication of complex metal nanoparticles on supports. Herein, the solid-phase synthesis strategy is developed to precisely synthesize uniformly distributed CoFe@FeO x core@shell nanoparticles. Fe atoms are preferentially exsolved from CoFe alloy bulk to the surface and then be carburized into a Fe x C shell under thermal syngas atmosphere, subsequently the formed Fe x C shell is passivated by air, obtaining CoFe@FeO x with a CoFe alloy core and a FeO x shell. This strategy is universal for the synthesis of MFe@FeO x (M = Co, Ni, Mn). The CoFe@FeO x exhibits bifunctional effect on regulating polysulfides as the separator coating layer for Li-S and Na-S batteries. This method could be developed into solid-phase synthetic systems to construct well distributed complex metal nanoparticles.

Sluggish surface reaction is a critical factor that strongly governs the efficiency of photocatalytic solar fuel production, particularly in CO 2 -to-ethanol photoconversion. Here, inspired by the principles underlying enzyme catalytic proficiency and specificity, we report a biomimetic photocatalyst that affords superior CO 2 -to-ethanol photoreduction efficiency (5.5 millimoles gram −1 hour −1 in average with 98.2% selectivity) distinctly surpassing the state of the art. The key is to create a class of catalytic pocket, which contains spatially organized NH 2 …Cu-Se(-Zn) multiple functionalities at close range, over ZnSe colloidal quantum wells. Such structure offers a platform to mimic the concerted cooperation between the active site and surrounding secondary/outer coordination spheres in enzyme catalysis. This is manifested by the chemical adsorption and activation of CO 2 via a bent geometry, favorable stabilization toward a variety of important intermediates, promotion of multielectron/proton transfer processes, etc. These results highlight the potential of incorporating enzyme-like features into the design of photocatalysts to overcome the challenges in CO 2 reduction.

Dietary deficiencies in essential micronutrients and other phytonutrients represent a global health and economic burden, contributing to “hidden hunger” and chronic diseases. While genome editing has been employed to improve individual nutritional traits in crops, multibiofortification through simultaneous modification of multiple distinct metabolic pathways is more challenging. Here, we designed a multiplex CRISPR-Cas strategy to edit five key genes in tomato: Sl7-DR2 , SlGAD3 , SlSGR1 , SlGGP1 , and SlGGP2 . This approach successfully generated quintuple mutant ( 5m ) tomato lines simultaneously biofortified with seven health-promoting compounds: vitamin D 3 (from 0 to 0.70 μg/g dry weight), vitamin C (up to 2.53-fold), provitamin A/β-carotene (up to 3.86-fold), α-carotene (up to 2.47-fold), lutein (up to 3.26-fold), lycopene (up to 7.07-fold), and γ-aminobutyric acid (GABA, up to 5.26-fold). Notably, these multibiofortified tomatoes exhibited no significant trade-offs in plant growth or fruit quality. Extracts from 5m tomatoes showed enhanced suppression of colorectal cancer cell proliferation in vitro. This antiproliferative effect was validated in vivo, where dietary supplementation with 5m tomato powder significantly inhibited tumor growth in a mouse xenograft model. Our work demonstrates an effective strategy for developing a next generation of “functional foods” through multibiofortification, creating a single, nutrient-dense crop that combats both micronutrient malnutrition and chronic diseases.

Abstract Single‐atom nanozymes (SAzymes) can effectively mimic the metal active centers of natural enzymes at the atomic level owing to their atomically dispersed active sites, thereby maximizing atom utilization efficiency and density of active sites. Hence, SAzymes can be considered the most promising candidates to replace natural enzymes. Herein, a PEGylated mesoporous Mn‐based single‐atom nanozyme (PmMn/SAE) employing a coordination‐assisted polymerization pyrolysis strategy that uses polydopamine for photothermal‐augmented nanocatalytic therapy is designed. PmMn/SAE exhibits excellent multiple enzymatic performance, including catalase‐like, oxidase‐like, and peroxidase (POD)‐like performance, due to the atomically dispersed Mn active species. As a result, PmMn/SAE not only catalyzes the decomposition of endogenous H 2 O 2 to generate O 2 for relieving hypoxia inside the tumor but also transfers electrons to O 2 to produce superoxide radicals to kill tumor cells. Meanwhile, PmMn/SAE is able to trigger Fenton‐like reactions to generate highly toxic hydroxyl radicals to induce cancer cell apoptosis. The POD‐like catalytic mechanism of mMn/SAE is revealed using experimental results and density functional theory. Furthermor, PmMn/SAE shows good photothermal conversion efficiency (η = 22.1%) in the second near‐infrared region (1064 nm). Both the in vitro and in vivo experimental results indicate that PmMn/SAE can effectively kill cancer cells through photothermal‐enhanced catalytic therapy.

ABSTRACT Data‐driven artificial intelligence provides strong technical support for addressing global energy and environmental issues. The powerful data processing and analysis capabilities of machine learning (ML) can quickly predict electrocatalytic performance, improving the efficiency of catalyst design and addressing the time‐consuming and inefficient nature of traditional catalyst design. By integrating ML with theoretical calculations and experiments, catalytic reaction processes can be precisely regulated. This not only accelerates the discovery of new catalysts but also drives the development of more efficient and environmentally friendly sustainable energy technologies. In this article, we discuss new approaches to discovering novel catalysts driven by ML, focusing on catalytic activity prediction, reaction energy barrier optimization, and the design of innovative catalytic materials. We systematically analysis the application of ML in the field of electrocatalysis and explore the future prospects of ML in this domain. We provide a comprehensive and in‐depth analysis of the application of ML in the field of electrocatalysis and explore its potential for future development.

Abstract Developing efficient and stable Pt‐based oxygen reduction reaction (ORR) electrocatalysts via both economical and controllable routes is critical for the practical application of electrochemical energy devices. Herein, a scalable, controllable, and general ambient‐O 2 ‐involved aqueous‐solution cultivating strategy to prepare Pt x M y (M = Ni, Fe, Co) bunched‐nanocages aerogels (BNCs AG) is demonstrated, based on a newly established high‐M‐to‐Pt‐precursor‐ratio‐and‐B‐incorporation‐facilitated M‐rich core and Pt‐rich shell hydrogel formation process. The Pt 83 Ni 17 BNCs AG shows prominent ORR performance with a mass activity (MA) of 1.95 A mg Pt −1 and specific activity of 3.55 mA cm −2 , which are 8.9‐times and 9.6‐times that of Pt supported on carbon (Pt/C), respectively. Particularly, the Pt 83 Ni 17 BNCs AG displays greatly enhanced durability (MA 82.6% retention) compared to Pt/C (MA 31.8% retention) after a 20 000‐cycles accelerated durability test. Systematic studies including density functional theory calculations uncover that the excellent activity is closely related to the optimized ligand and strain effects with the optimized Ni content in this aerogel; the outstanding durability is endowed by the lowered‐down Ni leaching with the optimized Pt/Ni ratio and the inhibited sintering due to its appropriate porosity. This work provides new perspectives on the development of electrocatalysts with both high performance and low cost.

Abstract Bismuth vanadate (BiVO 4 ) has been widely investigated as a photocatalyst or photoanode for solar water splitting, but its activity is hindered by inefficient cocatalysts and limited understanding of the underlying mechanism. Here we demonstrate significantly enhanced water oxidation on the particulate BiVO 4 photocatalyst via in situ facet-selective photodeposition of dual-cocatalysts that exist separately as metallic Ir nanoparticles and nanocomposite of FeOOH and CoOOH (denoted as FeCoO x ), as revealed by advanced techniques. The mechanism of water oxidation promoted by the dual-cocatalysts is experimentally and theoretically unraveled, and mainly ascribed to the synergistic effect of the spatially separated dual-cocatalysts (Ir, FeCoO x ) on both interface charge separation and surface catalysis. Combined with the H 2 -evolving photocatalysts, we finally construct a Z-scheme overall water splitting system using [Fe(CN) 6 ] 3−/4− as the redox mediator, whose apparent quantum efficiency at 420 nm and solar-to-hydrogen conversion efficiency are optimized to be 12.3% and 0.6%, respectively.

Abstract Nickel–iron‐based layered double hydroxides (NiFe LDHs) have attracted tremendous research and industrial interests for oxygen evolution reaction (OER) electrocatalysis. However, methodologies on simultaneous regulation of performance‐influencing factors remain scarce and their real synergistic effects are not clear enough. Herein, a versatile polyoxometallic acids (POMs) etching approach is reported to ingeniously reconstruct NiFe LDH, including 3D morphological nanotailoring, Fe 3+ and α‐Ni(OH) 2 active species reconfiguration, creation of multiple Ni, Fe, and O vacancies, and intercalation of POM polyanionic clusters. The experimental and theoretical data collaboratively unveil that control of the key performance‐influencing factors and their multiple synergistic mechanisms dominantly contribute to the step‐like OER performance enhancement. The reinforced electrocatalyst is further produced with low cost and high performance up to Ф180 mm in diameter, showing its feasibility and advancement of the promising configuration of NiFe LDH‐PMo12(+) II Ni@NiFe LDH(−) for alkaline anion‐exchange‐membrane electrode stack cells. Furthermore, to mathematically evaluate the evolution, a novel empirical formula is proposed for quantitative identification of structure–activity correlations, which offers an opportunity for first and fast reliability on materials screening.

An unprecedented molecular pumping cassette was designed and implemented for the construction of molecular necklaces, that is, radial [n]catenanes. The mechanism was fully confirmed on a model [2]pseudorotaxane, and the novel clipping-followed-by-pumping strategy was used to prepare a series of [n]catenanes (n = 2–5). A pair of [3]catenane diastereomers sequentially threaded with two different wheels was also accomplished. The success of utilizing molecular pumping to construct molecular necklaces offers new insights into complex molecular architectures and expands the application of molecular machines in synthesis.