Imaging Anisotropic Proton Intercalation in Photochromic MoO3.

Protonation represents a fundamental chemical process with promising applications in the fields of energy, environment, and memory devices. Probing the protonation mechanism, however, presents a formidable challenge owing to the elusiveness of intercalated protons. In this work, we utilize the atomic and electronic structure changes associated with protonation to directly image the proton intercalation pathways in α-MoO3 induced by UV illumination. We reveal the anisotropic intercalation behavior which is initiated by photocatalyzed water dissociation preferentially at the (001) edges and then propagates along the c axis, transforming α-MoO3 into HxMoO3 to realize photochromism. This photochromic process can be reversed via heating in air, leading to anisotropic proton deintercalation, also preferentially along the c axis. The observed anisotropic behavior can be attributed to the intrinsically low energy barriers for both proton migration along the c axis and water dissociation/formation at (001) edges.

Facet-Dependent Surface Restructuring on Nickel (Oxy)hydroxides: A Self-Activation Process for Enhanced Oxygen Evolution Reaction.

Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to ß-Ni(OH)2 catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals ß-Ni(OH)2 restructuring at the edge facets to form nanoporous Ni1-xO, which is Ni deficient containing Ni3+ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate ß-NiOOH phase in both the OER catalysis and Ni1-xO formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of ∼16-fold. Facilitated by such a self-activation process, the specially prepared ß-Ni(OH)2 with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO2, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.

Deciphering Anion-Modulated Solvation Structure for Calcium Intercalation into Graphite for Ca-Ion Batteries.

Co-intercalation reactions make graphite a feasible anode in Ca ion batteries, yet the correlation between Ca ion intercalation behaviors and electrolyte structure remains unclear. This study, for the first time, elucidates the pivotal role of anions in modulating the Ca ion solvation structures and their subsequent intercalation into graphite. Specifically, the electrostatic interactions between Ca ion and anions govern the configurations of solvated-Ca-ion in dimethylacetamide-based electrolytes and graphite intercalation compounds. Among the anions considered (BH4 -, ClO4 -, TFSI- and [B(hfip)4]-), the coordination of four solvent molecules per Ca ion (CN=4) leads to the highest reversible capacities and the fastest reaction kinetics in graphite. Our study illuminates the origins of the distinct Ca ion intercalation behaviors across various anion-modulated electrolytes, employing a blend of experimental and theoretical approaches. Importantly, the practical viability of graphite anodes in Ca-ion full cells is confirmed, showing significant promise for advanced energy storage systems.

Oxygen Vacancies Trigger Rapid Charge Transport Channels at the Engineered Interface of S-Scheme Heterojunction for Boosting Photocatalytic Performance.

Although oxygen vacancies (Ovs) have been intensively studied in single semiconductor photocatalysts, exploration of intrinsic mechanisms and in-depth understanding of Ovs in S-scheme heterojunction photocatalysts are still limited. Herein, a novel S-scheme photocatalyst made from WO3-Ov/In2S3 with Ovs at the heterointerface is rationally designed. The microscopic environment and local electronic structure of the S-scheme heterointerface are well optimized by Ovs. Femtosecond transient absorption spectroscopy (fs-TAS) reveals that Ovs trigger additional charge movement routes and therefore increase charge separation efficiency. In addition, Ovs have a synergistic effect on the thermodynamic and kinetic parameters of S-scheme photocatalysts. As a result, the optimal photocatalytic performance is significantly improved, surpassing that of single component WO3-Ov and In2S3 (by 35.5 and 3.9 times, respectively), as well as WO3/In2S3 heterojunction. This work provides new insight into regulating the photogenerated carrier dynamics at the heterointerface and also helps design highly efficient S-scheme photocatalysts.

Strain-Induced Surface Interface Dual Polarization Constructs PML-Cu/Bi12O17Br2 High-Density Active Sites for CO2 Photoreduction.

The insufficient active sites and slow interfacial charge transfer of photocatalysts restrict the efficiency of CO2 photoreduction. The synchronized modulation of the above key issues is demanding and challenging. Herein, strain-induced strategy is developed to construct the Bi-O-bonded interface in Cu porphyrin-based monoatomic layer (PML-Cu) and Bi12O17Br2 (BOB), which triggers the surface interface dual polarization of PML-Cu/BOB (PBOB). In this multi-step polarization, the built-in electric field formed between the interfaces induces the electron transfer from conduction band (CB) of BOB to CB of PML-Cu and suppresses its reverse migration. Moreover, the surface polarization of PML-Cu further promotes the electron converge in Cu atoms. The introduction of PML-Cu endows a high density of dispersed Cu active sites on the surface of PBOB, significantly promoting the adsorption and activation of CO2 and CO desorption. The conversion rate of CO2 photoreduction to CO for PBOB can reach 584.3 µmol g-1, which is 7.83 times higher than BOB and 20.01 times than PML-Cu. This work offers valuable insights into multi-step polarization regulation and active site design for catalysts.

Synthesis of core@shell catalysts guided by Tammann temperature.

Designing high-performance thermal catalysts with stable catalytic sites is an important challenge. Conventional wisdom holds that strong metal-support interactions can benefit the catalyst performance, but there is a knowledge gap in generalizing this effect across different metals. Here, we have successfully developed a generalizable strong metal-support interaction strategy guided by Tammann temperatures of materials, enabling functional oxide encapsulation of transition metal nanocatalysts. As an illustrative example, Co@BaAl2O4 core@shell is synthesized and tracked in real-time through in-situ microscopy and spectroscopy, revealing an unconventional strong metal-support interaction encapsulation mechanism. Notably, Co@BaAl2O4 exhibits exceptional activity relative to previously reported core@shell catalysts, displaying excellent long-term stability during high-temperature chemical reactions and overcoming the durability and reusability limitations of conventional supported catalysts. This pioneering design and widely applicable approach has been validated to guide the encapsulation of various transition metal nanoparticles for environmental tolerance functionalities, offering great potential to advance energy, catalysis, and environmental fields.