ABSTRACT Direct synthesis of urea through photocatalytic N 2 and CO 2 reduction (PNCR) offers a sustainable approach to mitigate CO 2 emissions and reduce energy consumption from urea production for industry and agriculture. However, achieving high yield of urea is limited by the high energy barrier for co‐reduction of N 2 and CO 2 with subsequent C–N coupling. Herein, we propose that the spin polarization of chiral mesostructured Mo doped Bi 2 WO 6 (CMMB) can facilitate the formation of triplet 3 NOH by regulating the parallel electron spin alignment and promote the separation and transfer of photogenerated carriers, leading to enhanced C–N formation. The incorporation of Mo sites into Bi 2 WO 6 promotes the adsorption and activation of N 2 . A state‐of‐the‐art urea yield was achieved without additives via PNCR on CMMB, surpassing the best‐reported inorganic catalyst by a significant margin. This study provides an effective strategy for designing catalyst structures for the green synthesis of organonitrogen compounds.

Quasicrystals have revolutionized our understanding of order in solids by demonstrating exotic structural and physicochemical properties with diverse potential applications. Despite the development of various theoretical models and experimental techniques to describe quasicrystal structures, the precise determination of local three dimensional (3D) arrangements of constituent atoms, or of secondary building units such as clusters or micelles, remains elusive. This challenge is particularly acute in self assembled soft matter quasicrystalline systems, where the complex assembly of molecular groups introduces additional defects and structural modulations. Herein, we report the first complete structural determination of self-assembled mesostructural dodecagonal quasicrystalline particles. Employing advanced electron tomography, combined with dedicated structural tracing and processing workflows, the 3D coordinates of all nodal sites were extracted. This approach reveals that the actual structure deviates from the conventionally assumed tetrahedral close packing geometry, exhibiting diverse coordination environments and displacive fluctuations. We identified and quantified rotational intergrowths arising from node exchange, as well as various defects and disorder, with these features discernible only through 3D analysis. Additionally, we propose a simplified two-layer stacking of isomorphic hexagonal model to form dodecagonal quasicrystal. This work advances our understanding of soft-matter dodecagonal quasicrystals and paves the way for detailed structural elucidation of self-assembled systems.

Zeolites exhibit complex structural heterogeneities that critically influence their catalytic behavior, yet these variations remain largely hidden within the crystal lattice. Here, we employ spatially resolved chemical etching combined with a multimodal, multiscale characterization approach to unravel four interrelated forms of heterogeneity in SAPO-34 crystals: defect zoning, silicon zoning, intergrowth zoning, and reactivity zoning. This approach integrates high-resolution SEM and TEM for 3D morphology and internal structure, structured illumination microscopy to map coke distribution on individually tracked crystals, and solid-state NMR (29Si, 1H, 19F, hyperpolarized 129Xe, and pulsed-field gradient) to probe framework environments, Brønsted acid sites, residual fluoride, micropore accessibility, and diffusion pathways. Using this top-down perspective, we reveal pronounced differences in structural stability among sub-structural units and uncover previously unrecognized X-shaped silicon zoning and an unprecedented CHA-AEI intergrowth structure with complex spatial organization. These coupled heterogeneities collectively govern crystal resistance to chemical etching and active site evolution during methanol-to-olefins conversion, thereby controlling catalytic selectivity and coke formation. This study provides an integrative, multiscale understanding of chemo-structural heterogeneity in zeolites, highlighting the potential of exploiting intrinsic imperfections for the rational design and optimization of advanced catalytic materials.

Abstract Triply periodic hyperbolic surfaces have been extensively investigated in various natural and artificial self-assembled systems and have attracted great attention because of their complexity and geometrical beauty. However, understanding their formation during bottom-up processes remains challenging because of the short lifetimes of structural intermediates and the soft nature of amphiphilic systems. Herein, we introduce UV light curing technology, which rapidly solidifies reaction intermediates without interfering with the final structure. The synthesis involves a miktoarm block copolymer, poly(ethylene oxide)-s-(polystyrene)2, with tetraethyl orthosilicate in a mixture of tetrahydrofuran and an aqueous HCl solution to form a silica scaffold with a shifted double diamond structure. By capturing intermediate phases at different reaction stages, we disclosed the following sequence of structural transformations: lamellar → perforated lamellar → single network → double diamond network → shifted double diamond after calcination. Our findings underscore the pivotal role of perforated lamellar structures and single networks as key intermediates, which exhibit instability conducive to transitioning into more stable double network configurations. This transformation also explains the coexistence of single and double networks observed in previous experiments and their unit cell parameter discrepancies. This research provides new insights into the formation of hyperbolic structures and the design of future self-assembly processes. This article is part of the theme issue ‘Geometry, materials and the imagination’.

ABSTRACT Acetic acid represents a pivotal target for CO 2 reduction due to its dual function as a carbon‐utilization product and industrial feedstock. However, photocatalytic CO 2 reduction (PCCR) to acetic acid typically suffers from low acetic acid yields and selectivity, constrained by competing reactions from ethanol and inefficient C–C coupling. Herein, we report a chiral mesostructured ZnIn 2 S 4 (CMZI) photocatalyst that achieves a remarkable acetic acid yield of 962 µmol g −1 h −1 with a high selectivity of 97.3%. This performance stems from synergistic chirality‐induced spin polarization and sulfur site catalysis. Spin polarization stabilizes the triplet OCCO intermediate to enhance C–C coupling, while sulfur sites on ZnIn 2 S 4 {102} facets thermodynamically and kinetically favor acetic acid formation. This work offers critical insights into catalytic strategies of the efficient synthesis of high‐value multicarbon products and expanding the variety of synthetic products from CO 2 reduction.

Gravitationally induced stratification during self-assembly often leads to density-driven vertical segregation, resulting in an inherent density gradient that severely limits the synthesis of metastable nanofilms requiring inverted architectures. Here we show an antigravity confined interfacial self-assembly approach based on a liquid-liquid interface formed between hydrophilic and hydrophobic porous membranes, where capillary forces suppress gravitational effects to enable precise molecular organization. Experimental data, supported by quantum chemistry, density functional theory, and Fick’s first law, demonstrate that capillary forces enhance local concentration and interaction probability, yielding highly ordered, stable nanofilms. Our approach achieves a 17-fold increase in film area than gravity-limited methods and a 109-fold improvement over unconfined techniques. These nanofilms exhibit the stability and mechanical property, showing promise for green enhanced oil recovery and multifunctional material development. Furthermore, our strategy offers a paradigm for nanofilm mechanical characterization, paving the way for future advances in the design and application of nanomaterials. Gravitationally induced stratification during self-assembly often leads to density driven vertical segregation limiting the synthesis of metastable nanofilms. Here, the authors address this limitation with an antigravity confined interfacial self-assembly synthesis where capillary forces dominate and enable precise molecular organization resulting in ordered and stable nanofilms.

The geometric design of structures with optimized physical and chemical properties is one of the core topics in materials science. However, designing new functional materials is challenging due to the vast number of existing and possible unknown structures to be enumerated and difficulties in mining the underlying correlations between structures and their properties. Here, we propose a universal method for periodic structural design and property optimization. The key in our approach is a deep-learning-assisted inverse Fourier transform, which enables the creation of arbitrary geometries within crystallographic space groups. It effectively explores extensive parameter spaces to identify ideal structures with desired properties. Taking the research of three-dimensional (3D) photonic structures as a case study, this method is capable of modelling numerous structures and identifying their photonic bandgaps in just a few hours. We confirmed the established knowledge that the widest photonic bandgaps exist in network morphologies, among which the single diamond (dia net) reigns supreme. Additionally, this method identified a rarely known lcs topology with excellent photonic properties, highlighting the infinitely extensible application boundaries of our approach. This work demonstrates the high efficiency and effectiveness of the Fourier-based method, advancing material design and providing insights for next-generation functional materials.

ATP is the core substance of energy metabolism in all forms of life. The chirality of d-ribose is essential for ATP's function, ensuring efficient molecular recognition, metabolic stability, and co-evolution with RNA in biological processes. However, origin of chirality of d-ribose is still unknown. Here, we demonstrate that wollastonite, an abundant Earth mineral, catalyzes the formose reaction between formaldehyde and glycolaldehyde and achieves high enantioselectivity (63.3%-91.3% ee) toward d-ribose. The lower energy barrier for the transition state of d-glyceraldehyde compared to that of l-glyceraldehyde, which possesses a similar configuration to glyceraldehyde, results in the enantioselective synthesis of ribose. Experimental and computational studies reveal that the surface chirality of wollastonite, which is characterized by its wavy atomic arrangement, selectively reduces the adsorption energy of the d-glyceraldehyde intermediate compared to its l-enantiomer. This preferential adsorption kinetically promotes the d-glyceraldehyde pathway and steers the reaction toward d-ribose. Our work establishes wollastonite as an intrinsically enantioselective mineral catalyst, provides a mechanistic foundation for prebiotic chiral selection toward d-ribose, and highlights surface design principles for asymmetric synthesis.

This review summarizes advances in multi-stimuli LCEs by dividing them into thermally and non-thermally coupled systems from the perspective of thermal phase transition, where their responsive coupling modes/mechanisms and applications are discussed.

Structural colouration with narrow spectral photonic bandwidth and high reflectivity is of critical importance for modern optical applications, including displays, laser systems, and optical sensing, etc. Achieving such angle independent colouration typically relies on polycrystalline or inherent structural disorder. However, balancing angular uniformity with high brightness and strong colour contrast remains challenging. Herein, we uncover the structural origin of the spectacular bright, angle-independent blue colouration of Hypochrysops polycletus, a sapphire-like Royal Jewel butterfly. Three-dimensional (3D) electron microscopy reveals that the dorsal wing scale has a single diamond structure, a 3D photonic crystal previously documented only in beetles and weevils. The crystal domains form an extraordinary quasi sinusoidal surface geometry with a distinct template morphology-guided arrangement. Unlike typically thicker biophotonic structures that support multiple high symmetry stopbands, this design contains only 3-4 unit cells in the propagation direction. Its optical response is dominated by the fundamental stopband, with two dominant scattering mechanisms: specular reflection at the 111 inclined sidewalls of the hierarchical structure, and funnelling into localised quasi-normal modes enabled by a strongly anisotropic Bloch transport. By mimicking these features with two-photon polymerisation, we artificially reproduced the optical response in the infrared region. The study opens a pathway towards bioinspired brilliant diffuse colouration and angle-robust photonic devices.

Direct synthesis of urea through photocatalytic N2 and CO2 reduction (PNCR) offers a sustainable approach to mitigate CO2 emissions and reduce energy consumption from urea production for industry and agriculture. However, achieving high yield of urea is limited by the high energy barrier for co-reduction of N2 and CO2 with subsequent C-N coupling. Herein, we propose that the spin polarization of chiral mesostructured Mo doped Bi2WO6 (CMMB) can facilitate the formation of triplet 3NOH by regulating the parallel electron spin alignment and promote the separation and transfer of photogenerated carriers, leading to enhanced C-N formation. The incorporation of Mo sites into Bi2WO6 promotes the adsorption and activation of N2. A state-of-the-art urea yield was achieved without additives via PNCR on CMMB, surpassing the best-reported inorganic catalyst by a significant margin. This study provides an effective strategy for designing catalyst structures for the green synthesis of organonitrogen compounds.

Guanine crystals are renowned as one of the most appealing biogenic organic optical crystals in living organisms, widely known for their high refractive index, rivaling inorganic crystals. Since their optical excellence is governed by specific morphologies, it is imperative to comprehend the methods for controlling the growth and assembly of guanine crystals. However, the artificial control over their morphology, especially in repeating the biogenic ones, remains a formidable challenge. Herein, we present a biomimetic synthesis strategy to engineer hierarchical guanine crystal polymorphs by controlling the primary nuclei growth processes, followed by the structural modulation under the competition of hydrogen bonding and π-π interactions. Five typical crystal morphologies, ranging from dense spherical polycrystalline aggregates to thin flake crystals, were successfully synthesized. The crystallization mechanism was analyzed using principal component analysis (PCA) method in machine learning technology, where the crystal nucleation behaviors were found to be critical in determining the crystal hierarchies and a three-dimensional synthesis-field diagram mapping 30,000 possible parameter combinations has been predicted. Additionally, these morphologies significantly affect the birefringence and the reflection of the crystals. This work provides a way for tailoring biogenic crystals through precise crystal nucleation regulation and growth-directed assemblies.

Acetic acid represents a pivotal target for CO2 reduction due to its dual function as a carbon-utilization product and industrial feedstock. However, photocatalytic CO2 reduction (PCCR) to acetic acid typically suffers from low acetic acid yields and selectivity, constrained by competing reactions from ethanol and inefficient C-C coupling. Herein, we report a chiral mesostructured ZnIn2S4 (CMZI) photocatalyst that achieves a remarkable acetic acid yield of 962 µmol g-1 h-1 with a high selectivity of 97.3%. This performance stems from synergistic chirality-induced spin polarization and sulfur site catalysis. Spin polarization stabilizes the triplet OCCO intermediate to enhance C-C coupling, while sulfur sites on ZnIn2S4 {102} facets thermodynamically and kinetically favor acetic acid formation. This work offers critical insights into catalytic strategies of the efficient synthesis of high-value multicarbon products and expanding the variety of synthetic products from CO2 reduction.

Catalytic cracking of light alkanes represents an important route to produce light olefins with reduced energy input and flexible product selectivity with respect to conventional steam cracking. Herein, we demonstrate the synthesis of ZSM-5 zeolites using a series of n-heptane cracking transition state-mimicking organic structure-directing agents (OSDAs), i.e., N,N,N-trimethylpentylammonium (TMPA), N-ethyl-N,N-dimethylbutylammonium (EDMBA), and N-Ethyl-N,N-dimethylpentylammonium (EDMPA) under inorganic cation-free conditions. MFI zeolites derived from TMPA and EDMBA crystallize as thin nanoplates of 80-130 nm and 70-110 nm, in thickness, respectively, as a result of anisotropic growth along the bc plane, and the intergrowth of nanoplates constructs a house-of-cards architecture with penetrable voids. EDMPA-generated sample forms an alternative intergrowth made up of ship-like crystals of 1.0 to 1.6 mu m, without auxiliary porosity. The decrease in crystal dimension, increase in surface area, and integration of macropores can boost the diffusion property and an incremental order of diffusion characteristic time constants: ZSM-5-C < ZSM-5-TMPA < ZSM-5-EDMPA < ZSM-5-EDMBA has been measured using 2-methylhexane as a probe molecule. The site densities for intermediate-to-strong Br & oslash;nsted acid increase in the order of ZSM-5-TMPA < ZSM-5-EDMPA < ZSM-5-EDMBA, which coincides with their crystallinity. In n-heptane cracking, the light olefin selectivity and catalyst lifetime have been boosted, and ZSM-5-EDMBA outperforms others due to the presence of more catalytically important strong acid sites, favorable center C-C cleavage, and reduced residence time for primary olefin products that suppresses their further conversion into aromatics and coke precursors. The use of transition-state-mimicking OSDAs to generate zeolite provides an effective strategy for cracking catalyst design toward light olefin production.

Co-templating synthesis of MSE zeolites with reduced structure-directing agents, shortened crystallization time and tailored acidity is presented. Enhanced catalyst stability and light olefin selectivity have been attained for n -heptane cracking.

Mesoporous zeolite-anchored atomically dispersed metal (ADM) catalysts are capable of overcoming diffusion limitations, promoting mass transfer, and exposing more active sites. These features make them one of the most ideal heterogeneous catalysts. However, introducing both mesoporosity and ADM species into zeolite structures while avoiding metal clustering remains a significant challenge. Herein, we report the hierarchical MFI zeolite encapsulated atomically dispersed nickel species using a ligand-protected in situ synthesis strategy with a tri-functional template. This template incorporates quaternary ammonium hydrophilic head groups linked to central metal-coordinated porphyrins by alkyl chains, which guide the formation of mesoporous MFI zeolite structure while simultaneously suppressing nickel clustering. The resulting catalyst exhibits a hierarchical architecture comprising MFI nanosheets with enhanced 90° rotational intergrowth, and the dispersed Ni sites are evenly distributed within the zeolite framework. The catalyst exhibited a high activity and efficient utilization of Ni in probing CO2 hydrogenation reaction. The use of functionalized metal-coordinated porphyrins as a structure-directing agent to generate zeolite-supported metal catalysts is transferable, which opens new possibilities for controlling zeolite architecture.

Designing Fischer-Tropsch synthesis (FTS) catalysts to selectively produce liquid hydrocarbon fuels is a crucial challenge. Herein, we selectively introduced Co nanoparticles (NPs) into the micropores and mesopores of an ordered mesoporous MFI zeolite (OMMZ) through impregnation, which controlled the carbon number distribution in the FTS products by tuning the position of catalytic active sites in differently sized pores. The Co precursors coordinated by acetate with a size of 9.4 x 4.2 x 2.5 & Aring; and by 2,2'-bipyridine with a size of 9.5 x 8.7 x 7.9 & Aring;, smaller and larger than the micropores (ca. 5.5 & Aring;) of MFI, made the Co species incorporated in OMMZ's micropores and mesopores, respectively. The carbon number products synthesized with the Co NPs confined in mesopores were larger than that in micropores. The high jet and diesel selectivities of 66.5% and 65.3% were achieved with Co NPs confined in micropores and mesopores of less acidic Na-type OMMZ, respectively. Gasoline and jet selectivities of 76.7% and 70.8% were achieved with Co NPs confined in micropores and mesopores of H-type OMMZ with Br & ouml;nsted acid sites, respectively. A series of characterizations revealed that the selective production of diesel and jet fuels was due to the C-C cleavage suppressing of heavier hydrocarbons by the Co NPs located in mesopores. Published by Elsevier B.V. All rights reserved.

Reduction and fixation of CO2 in natural systems via solar energy generates diverse products, ranging from small molecules to biomolecules. To date, only a few multicarbon species have been obtained by artificial CO2 photoreduction1-5, especially abiotic photosynthesis of biomolecules with various functional groups, which has long been a fundamental yet challenging issue. Herein, we report the photocatalytic synthesis of amino acids from CO2 and NH3 on a chiral mesostructured ZnS (CMZ) nanosphere, which is constructed by arrays of chiral nanorods. Serine (Ser) is the main component of various amino acids, with an enantiomeric excess (ee) greater than 96% and a total yield of over 30 μmol gcat-1. The Ser formation pathway could be accessed through *OCCO intermediates due to C-C coupling, as demonstrated by experimental data. Chiral-induced spin polarization of CMZ has been speculated to facilitate the separation of photogenerated carriers and the production of stable triplet OCCO. Different activation energies of reduction reactions driven by the spin-polarized electrons in CMZ lead to the formation of enantiomeric amino acids. Our findings will inspire new perspectives in catalytic theory and the formation of chiral biomolecules in artificial synthesis and nature.

Multipore MSE zeolite possesses three-dimensional (3D) pore-network constructed of interconnected 10- and 12membered rings (MRs), i.e., between its broadly used cousins, medium-pore MFI and large-pore Beta, and has exhibited promising catalytic performances in catalytic cracking reactions. One major bottleneck for the commercial deployment of MSE zeolite is the prohibitive production cost due to the use of expensive organic structure directing agent (OSDA). We report here a designed inexpensive OSDA, dispiro[piperidine-1,2 '(1 ',2 ',3 ',5 ',6 ',7 '-hexahydrobenzo [1,2-c: 4, 5-c '] dipyrrolium)-6 ',1 ''-piperidine, that can better stabilize the framework and is specific to the generation of MSE in the presence of K+. The OSDA is occluded in the supercage and 12-MR straight channel, while the K+ occupies the 625442 cage, affording high crystallinity and strong acidity. The dealuminated zeolite shows improved light olefin (in particular, propylene) selectivity and catalyst lifetime in catalytic cracking of typical naphtha pool molecule n-heptane. The recipe is a step forward for the specific, low-cost generation of the MSE zeolite and may inspire more investigations on its catalytic applications.

Zeolitic nanosheets possess great potential in catalysis due to their enhanced transport property and accessibility toward bulky molecules compared to conventional micron- meter scale crystals. However, the generation of Beta zeolite nanosheets, which are crucial for industrial catalysis, is still challenging for its intergrowth nature. In this work, aluminosilicate Beta nanosheets of ca. 16 nm thick with house-of-cards architecture are generated using a special polycationic organic structure directing agent (OSDA), [-N+(CH3)2-C5H10-N+(CH3)2-C6H12-]n[Br-]2n, in greener hydroxide media. Transmission electron microscopy and electron tomography reconstruction revealed that the nanosheets are composed of unprecedented intergrowth of polymorphs B and polymorph C (i.e., BEC topology), possessing only straight micropore channels. 2D 29Si{1H} and 27Al{1H} heteronuclear correlation NMR spectra reveal that the framework Al atoms are mainly situated close to the ammonium moieties of the OSDA inside straight channels, owing to a strong OSDA-framework attraction. The selectivities of ethylene, propylene and catalyst lifetime have been promoted in n-heptane cracking, due to stronger acidity and enhanced diffusion property. Moreover, the architecture is robust toward deep dealumination and Ti- modification, allowing it to be a superior catalyst in cyclohexene epoxidation. The polycation OSDA design concept and the recipe for Beta nanosheets may find broader applications in catalysis.