Spatiotemporal Heterogeneity of Temperature and Catalytic Activation within Individual Catalyst Particles.

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.

Significantly Enhanced Energy-Saving H2 Production Coupled with Urea Oxidation by Low- and Non-Pt Anchored on NiS-Based Conductive Nanofibers.

Rational designing electrocatalysts is of great significance for realizing high-efficiency H2 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 H2 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.

Silica Confinement for Stable and Magnetic Co-Cu Alloy Nanoparticles in Nitrogen-Doped Carbon for Enhanced Hydrogen Evolution.

Ammonia borane (AB) with 19.6 wt % H2 content is widely considered a safe and efficient medium for H2 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 (CoxCu1-x@NC@mSiO2) were synthesized using a facile mSiO2-confined thermal pyrolysis strategy. The obtained product, an optimized Co0.8Cu0.2@NC@mSiO2 catalyst, exhibits enhanced performance with a turnover frequency of 240.9 molH2 ⋅ molmetal ⋅ min-1 for AB hydrolysis at 298 K, surpassing most noble-metal-free catalysts. Moreover, Co0.8Cu0.2@NC@mSiO2 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.

Directional Construction of Active Naphthalenic Species within SAPO-34 Crystals toward More Efficient Methanol-to-Olefin Conversion.

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.

Control of Surface Barriers in Mass Transfer to Modulate Methanol-to-Olefins Reaction over SAPO-34 Zeolites.

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.

One-Dimensional Single-Crystal Mesoporous TiO2 Supported CuW6O24 Clusters as Photocatalytic Cascade Nanoreactor for Boosting Reduction of CO2 to CH4.

Constructing nanoreactors with multiple active sites in well-defined crystalline mesoporous frameworks is an effective strategy for tailoring photocatalysts to address the challenging of CO2 reduction. Herein, one-dimensional (1-D) mesoporous single-crystal TiO2 nanorod (MS-TiO2-NRs, ≈110 nm in length, high surface area of 117 m2 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 TiO2 can be further tuned to polycrystalline fan- and flower-like morphologies with different oxygen vacancies (Ov). The integration of single-crystal nature and mesopores with exposed oxygen vacancies make the rod-like TiO2 nanoreactors exhibit a high-photocatalytic CO2 reduction selectivity to CO (95.1%). Furthermore, photocatalytic cascade nanoreactors by in situ incorporation of CuW6O24 (W-Cu) clusters onto MS-TiO2-NRs via Ov are designed and synthesized, which improved the CO2 adsorption capacity and achieved two-step CO2-CO-CH4 photoreduction. The second step CO-to-CH4 reaction induced by W-Cu sites ensures a high generation rate of CH4 (420.4 µmol g-1 h-1), along with an enhanced CH4 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.

Hyperloop-like diffusion of long-chain molecules under confinement.

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.

Clarifying the Temperature-Dependent Lithium Deposition/Stripping Process and the Evolution of Inactive Li in Lithium Metal Batteries.

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.

Constructing asymmetric double-atomic sites for synergistic catalysis of electrochemical CO2 reduction.

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 TeN2-CuN3 double-atomic site catalyst, which is analyzed via full-range synchrotron pair distribution function. In electrochemical CO2 reduction, the catalyst features a synergistic mechanism with the double-atomic site activating two key molecules: operando spectroscopy confirms that the Te center activates CO2, and the Cu center helps to dissociate H2O. The experimental and theoretical results reveal that the TeN2-CuN3 could cooperatively lower the energy barriers for the rate-determining step, promoting proton transfer kinetics. Therefore, the TeN2-CuN3 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.

Directed transforming of coke to active intermediates in methanol-to-olefins catalyst to boost light olefins selectivity.

Methanol-to-olefins (MTO), the most important catalytic process producing ethylene and propylene from non-oil feedstocks (coal, natural gas, biomass, CO2, 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 H2 and negligible CO2 as byproducts from regeneration under industrial-alike continuous operations. This strategy significantly boosts the economics and sustainability of MTO process.

Stabilizing the framework of SAPO-34 zeolite toward long-term methanol-to-olefins conversion.

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 27Al, 31P MAS NMR, and 2D 31P-27Al 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.

Imaging spatiotemporal evolution of molecules and active sites in zeolite catalyst during methanol-to-olefins reaction.

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.