Search

Translation and rotation are the two most fundamental forms of diffusion, yet their coupling mechanism is not clear, especially under confinement. Here, we provided evidence of the coupling between rotation and translation using a substituted benzene molecule as an example. A counterintuitive behavior was observed where the movement of the smaller molecule with an asymmetric shape was unexpectedly slower than the larger one with a symmetric shape in confined channels of zeolite. We showed that this diffusion behavior was caused by the presence of the specific and selective interaction of the asymmetric guest with the pores, which increased the local restricted residence time, thus inhibiting the translation under confinement, as further confirmed by dynamic breakthrough curves, uptake measurements, quasi-elastic neutron scattering, and 2 H solid-state NMR techniques. Our work correlated asymmetric rotation and diffusion under a confined environment, which enriched our understanding of the coupling between rotation and translation and could shed light on a fundamental understanding of the diffusion process., Competing Interests: Competing interests: The authors declare no competing interests., (© 2025. The Author(s).)

Developing highly efficient non-iridium-based active sites for acidic water splitting is still a huge challenge. Herein, unique Ru-B-Cr moieties have been constructed in RuO 2 nanofibers (NFs) to activate Ru sites for water electrolysis, which overcomes the bottleneck of RuO 2 -based catalysts usually possessing low activity for the hydrogen evolution reaction (HER) and poor stability for the oxygen evolution reaction (OER). The fabricated Cr, B-doped RuO 2 NFs exhibit low overpotentials of 205 and 379 mV for acidic HER and OER at 1 A cm -2 with outstanding stability lasting 1000 and 188 h, respectively. The assembled acidic electrolyzer also possesses great hydrogen production efficiency and durability at a high current density. Experimental and theoretical explorations reveal that the formation of Ru-B-Cr moieties effectively optimizes the atomic configurations and modulates the adsorption/desorption free energy of reaction intermediates to achieve exceptional HER and OER performance.

Zeolites, the most technically important crystalline microporous materials, are indispensable cornerstones of chemical engineering because of their remarkable catalytic properties and adsorption capabilities. Numerous studies have demonstrated that the hierarchical engineering of zeolites can maximize accessible active sites and improve mass transport, which significantly decreases the internal diffusion limits to achieve the desired performance. However, the construction of hierarchical zeolites with ordered alignments and size-controlled substructures in a convenient way is highly challenging. Herein, we develop a facile procedure using two common structure-directing agents, tetrapropylammonium hydroxide (TPAOH) and tetraethylammonium hydroxide (TEAOH), to synthesize hierarchically aligned ZSM-5 (Hie-ZSM-5) crystals with a -axis alignment substructures of controllable size. The control of the substructure size (α) in the range of 10-60 nm and the corresponding similarity ( r = α/β, where β is the size of Hie-ZSM-5) ranging from 0.004 to 0.033 can be tuned by varying the Si/Al ratios (40-120). A systematic investigation of the overall crystallization process, using time-dependent XRD, SEM, TEM, and solid-state magic-angle spinning NMR ( 13 C, 27 Al, 29 Si) methods, enable us to construct a solid mechanism for the generation of Hie-ZSM-5. Most importantly, directional transport in the unique structures of Hie-ZSM-5 efficiently enhances mass diffusion, as well as catalytic activity and stability. These findings improve our understanding of the zeolite crystallization process and inspire novel methods for the rational design of hierarchical zeolites.

Constructing nanoreactors with multiple active sites in well-defined crystalline mesoporous frameworks is an effective strategy for tailoring photocatalysts to address the challenging of CO 2 reduction. Herein, one-dimensional (1-D) mesoporous single-crystal TiO 2 nanorod (MS-TiO 2 -NRs, ≈110 nm in length, high surface area of 117 m 2 g -1 , and uniform mesopores of ≈7.0 nm) based nanoreactors are prepared via a droplet interface directed-assembly strategy under mild condition. By regulating the interfacial energy, the 1-D mesoporous single-crystal TiO 2 can be further tuned to polycrystalline fan- and flower-like morphologies with different oxygen vacancies (O v ). The integration of single-crystal nature and mesopores with exposed oxygen vacancies make the rod-like TiO 2 nanoreactors exhibit a high-photocatalytic CO 2 reduction selectivity to CO (95.1%). Furthermore, photocatalytic cascade nanoreactors by in situ incorporation of CuW 6 O 24 (W-Cu) clusters onto MS-TiO 2 -NRs via O v are designed and synthesized, which improved the CO 2 adsorption capacity and achieved two-step CO 2 -CO-CH 4 photoreduction. The second step CO-to-CH 4 reaction induced by W-Cu sites ensures a high generation rate of CH 4 (420.4 µmol g -1 h -1 ), along with an enhanced CH 4 selectivity (≈94.3% electron selectivity). This research provides a platform for the design of mesoporous single-crystal materials, which potentially extends to a range of functional ceramics and semiconductors for various applications., (© 2024 Wiley‐VCH GmbH.)

Ammonia borane (AB) with 19.6 wt % H 2 content is widely considered a safe and efficient medium for H 2 storage and release. Co-based nanocatalysts present strong contenders for replacing precious metal-based catalysts in AB hydrolysis due to their high activity and cost-effectiveness. However, precisely adjusting the active centers and surface properties of Co-based nanomaterials to enhance their activity, as well as suppressing the migration and loss of metal atoms to improve their stability, presents many challenges. In this study, mesoporous-silica-confined bimetallic Co-Cu nanoparticles embedded in nitrogen-doped carbon (Co x Cu 1-x @NC@mSiO 2 ) were synthesized using a facile mSiO 2 -confined thermal pyrolysis strategy. The obtained product, an optimized Co 0.8 Cu 0.2 @NC@mSiO 2 catalyst, exhibits enhanced performance with a turnover frequency of 240.9 mol H2  ⋅ mol metal  ⋅ min -1 for AB hydrolysis at 298 K, surpassing most noble-metal-free catalysts. Moreover, Co 0.8 Cu 0.2 @NC@mSiO 2 demonstrates magnetic recyclability and extraordinary stability, with a negligible decline of only 0.8 % over 30 cycles of use. This enhanced performance was attributed to the synergistic effect between Co and Cu, as well as silica confinement. This work proposes a promising method for constructing noble-metal-free catalysts for AB hydrolysis., (© 2024 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

Temperature is a critical parameter in chemical conversion, significantly affecting the reaction kinetics and thermodynamics. Measuring temperature inside catalyst particles of industrial interest (∼micrometers to millimeters), which is crucial for understanding the evolution of chemical dynamics at catalytic active sites during reaction and advancing catalyst designs, however, remains a big challenge. Here, we propose an approach combining two-photon confocal microscopy and state-of-the-art upconversion luminescence (UL) imaging to measure the spatiotemporal-resolved temperature within individual catalyst particles in the industrially significant methanol-to-hydrocarbons reaction. Specifically, catalyst particles containing zeolites and functional nanothermometers were fabricated using microfluidic chips. Our experimental results directly demonstrate that the zeolite density and particle size can alter the temperature distribution within a single catalyst particle. Importantly, the observed temperature heterogeneity plays a decisive role in the activation of the reaction intermediate and the utilization of active sites. We expect that this work opens a venue for unveiling the reaction mechanism and kinetics within industrial catalyst particles by considering temperature heterogeneity.

Rational designing electrocatalysts is of great significance for realizing high-efficiency H 2 production in the water splitting process. Generally, reducing the usage of precious metals and developing low-potential nucleophiles oxidation reaction to replace anodic oxygen evolution reaction (OER) are efficient strategies to promote H 2 generation. Here, NiS-coated nickel-carbon nanofibers (NiS@Ni-CNFs) are prepared for low-content Pt deposition (Pt-NiS@Ni-CNFs) to attain the alkaline HER catalyst. Due to the reconfiguration of NiS phase and synergistic effect between Pt and nickel sulfides, the Pt-NiS@Ni-CNFs catalyst shows a high mass activity of 2.74-fold of benchmark Pt/C sample. In addition, the NiS@Ni-CNFs catalyst performs a superior urea oxidation reaction (UOR) activity with the potential of 1.366 V versus reversible hydrogen electrode (RHE) at 10 mA cm -2 , which demonstrates the great potential in the replacement of OER. Thus, a urea-assisted water splitting electrolyzer of Pt-NiS@Ni-CNFs (cathode)||NiS@Ni-CNFs (anode) is constructed to exhibit small voltages of 1.44 and 1.65 V to reach 10 and 100 mA cm -2 , which is much lower than its overall water splitting process, and presents a 6.5-fold hydrogen production rate enhancement. This work offers great opportunity to design new catalysts toward urea-assisted water splitting with significantly promoted hydrogen productivity and reduced energy consumption., (© 2023 Wiley-VCH GmbH.)

The deposition/stripping behavior of lithium metal is intriguing, and the associated formation of inactive lithium at various temperatures remains elusive, which hinders the practical application of lithium metal batteries. Here, utilizing the variable-temperature operando solid-state nuclear magnetic resonance (SS NMR) technique, we reveal the temperature effects on the lithium microstructure evolution in a carbonate-based electrolyte system. In addition, the mass spectrometry titration (MST) method is used to quantify the evolution of inactive lithium components, including dead lithium, solid electrolyte interface (SEI), and lithium hydride (LiH). Combined SS NMR and MST results show that the morphology of lithium metal is reasonably correlated to the amount of inactive Li formed. At low/ambient temperature, the lithium microstructure has a similar evolution pattern, and its poor morphology leads to a large amount of dead lithium, which dominates capacity loss; however, at high temperature large and dense lithium deposits form with less dead Li detected, and the intensified electrolyte consumption in SEI formation is the major cause for capacity loss. Our phase-field simulation results reveal that the compact lithium deposition formed at higher temperature is due to the more uniformly distributed electric field and Li + concentration. Lastly, two strategies in forming a dense Li deposit are proposed and tested that show performance-enhancing results.

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., (© 2023. Springer Nature Limited.)

The ultrafast transport of adsorbates in confined spaces is a goal pursued by scientists. However, diffusion will be generally slower in nano-channels, as confined spaces inhibit motion. Here we show that the movement of long-chain molecules increase with a decrease in pore size, indicating that confined spaces promote transport. Inspired by a hyperloop running on a railway, we established a superfast pathway for molecules in zeolites with nano-channels. Rapid diffusion is achieved when the long-chain molecules keep moving linearly, as well as when they run along the center of the channel, while this phenomenon do not exist for short-chain molecules. This hyperloop-like diffusion is unique for long-chain molecules in a confined space and is further verified by diffusion experiments. These results offer special insights into molecule diffusion under confinement, providing a reference for the selection of efficient catalysts with rapid transport in the industrial field., (© 2023. The Author(s).)

Olefin selectivity and catalyst lifetime are two key metrics for industrial methanol-to-olefin catalysts. Currently, it is very difficult to obtain high olefin selectivity and long catalyst lifetime at the same time. Herein, a feasible strategy combining precoking and steaming to directionally construct the active naphthalenic species within the crystal center of the SAPO-34 catalyst has been developed, which can not only promote the lower olefin selectivity to ∼89% (ethylene and propylene) but also prolong the catalyst lifetime by ∼3.7-fold in the methanol-to-olefin conversion. Structured illumination microscopy, in situ ultraviolet-visible spectroscopy, and online mass spectrometry elucidate the spatiotemporal distribution and evolution of the naphthalenic species during the precoking and steaming processes. This one-stone-two-birds strategy is applicable to a commercial SAPO-34 catalyst containing a binder, demonstrating its bright prospect in the methanol-to-olefin industry.

As a commercial MTO catalyst, SAPO-34 zeolite exhibits excellent recyclability probably due to its intrinsic good hydrothermal stability. However, the structural dynamic changes of SAPO-34 catalyst induced by hydrocarbon pool (HP) species and the water formed during the MTO conversion as well as its long-term stability after continuous regenerations are rarely investigated and poorly understood. Herein, the dynamic changes of SAPO-34 framework during the MTO conversion were identified by 1D 27 Al, 31 P MAS NMR, and 2D 31 P- 27 Al HETCOR NMR spectroscopy. The breakage of T-O-T bonds in SAPO-34 catalyst during long-term continuous regenerations in the MTO conversion could be efficiently suppressed by pre-coking. The combination of catalyst pre-coking and water co-feeding is established to be an efficient strategy to promote the catalytic efficiency and long-term stability of SAPO-34 catalysts in the commercial MTO processes, also sheds light on the development of other high stable zeolite catalyst in the commercial catalysis., (© 2021. The Author(s).)

Methanol-to-olefins (MTO), the most important catalytic process producing ethylene and propylene from non-oil feedstocks (coal, natural gas, biomass, CO 2 , etc.), is hindered by rapid catalyst deactivation due to coke deposition. Common practice to recover catalyst activity, i.e. removing coke via air combustion or steam gasification, unavoidably eliminates the active hydrocarbon pool species (HCPs) favoring light olefins formation. Density functional theory calculations and structured illumination microscopy reveal that naphthalenic cations, active HCPs enhancing ethylene production, are highly stable within SAPO-34 zeolites at high temperature. Here, we demonstrate a strategy of directly transforming coke to naphthalenic species in SAPO-34 zeolites via steam cracking. Fluidized bed reactor-regenerator pilot experiments show that an unexpectedly high light olefins selectivity of 85% is achieved in MTO reaction with 88% valuable CO and H 2 and negligible CO 2 as byproducts from regeneration under industrial-alike continuous operations. This strategy significantly boosts the economics and sustainability of MTO process.

Mass transfer of guest molecules has a significant impact on the applications of nanoporous crystalline materials and particularly shape-selective catalysis over zeolites. Control of mass transfer to alter reaction over zeolites, however, remains an open challenge. Recent studies show that, in addition to intracrystalline diffusion, surface barriers represent another transport mechanism that may dominate the overall mass transport rate in zeolites. We demonstrate that the methanol-to-olefins (MTO) reaction can be modulated by regulating surface permeability in SAPO-34 zeolites with improved chemical liquid deposition and acid etching. Our results explicitly show that the reduction of surface barriers can prolong catalyst lifetime and promote light olefins selectivity, which opens a potential avenue for improving reaction performance by controlling the mass transport of guest molecules in zeolite catalysis., (© 2020 Wiley-VCH GmbH.)

Direct visualization of spatiotemporal evolution of molecules and active sites during chemical transformation in individual catalyst crystal will accelerate the intuitive understanding of heterogeneous catalysis. So far, widespread imaging techniques can only provide limited information either with large probe molecules or in model catalyst of large size, which are beyond the interests of industrial catalysis. Herein, we demonstrate a feasible deep data approach via synergy of multiscale reaction-diffusion simulation and super-resolution structured illumination microscopy to  illustrate the dynamical evolution of spatiotemporal distributions of gas molecules, carbonaceous species and acid sites in SAPO-34 zeolite crystals of several micrometers that are typically used in industrial methanol-to-olefins process. The profound insights into the inadequate utilization of activated acid sites and rapid deactivation are unveiled. The notable elucidation of molecular reaction-diffusion process  at the scale of single catalyst crystal via this approach opens an interesting method for mechanism study in materials synthesis and catalysis.