Low Barrier Research Articles

Unraveling the Mechanism and Influence of Auxiliary Ligands on the Isomerization of Neutral [P,O]-Chelated Nickel Complexes for Olefin Polymerization.

The copolymerization of ethylene with polar monomers presents a significant challenge. While palladium catalysts have shown promise, nickel catalysts are more economical but suffer from poor activity. Previous studies suggest that the isomerization step involved in the nickel-catalyzed polymerization may influence the catalyst activities. Herein, we explore the isomerization mechanisms of two phosphine-phenoxide-ligated catalysts using density functional theory (DFT) studies. We found that out of dissociative, tetrahedral, and associative mechanisms, the associative mechanism is the likeliest, with a pendant methoxy oxygen atom from the ligand to fulfill the fifth coordination site on nickel before Berry pseudorotation. The effect of varying auxiliary ligands on the activation barrier heights was also investigated and found that electron-releasing alkyl groups on substituted pyridine ligands have diminished electronic influence on pseudorotational barriers, but if present at the ortho-positions, will elevate the barriers due to larger steric influences. The electron-withdrawing groups on the ligand result in weaker ligand binding and lower pseudorotational barriers. These insights into the mechanisms of cis-trans isomerization and auxiliary ligand effects may offer valuable guidance for optimizing catalyst performance in copolymerization processes by lowering the barrier of isomerization by fine-tuning the steric and electronic influences of auxiliary ligands and enhancing overall copolymerization efficiency.

In situ construction of MOF derived CoNC anchored on N-doped carbon xerogel sphere as efficient bifunctional ORR/OER electrocatalyst for Zn-air batteries

Electrocatalytic materials with dual functions of oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) have received increasing attention in the field of zinc-air batteries (ZABs) research. In this study, bifunctional CoNC@NCXS catalysts were prepared by anchoring Co and N co-doped CoNC on N-doped carbon xerogel sphere (NCXS) based on the spatially confined domain effect and in-situ doping technique. CoNC@NCXS exhibited excellent ORR/OER activity in alkaline electrolytes with the ORR onset potential of 0.99 V, the half-wave potential (E1/2) of 0.78 V at 10 mA cm−2 and the OER overpotential of 360 mV at 10 mA cm−2. These excellent catalytic activities were derived from constructing composite active structures and enhancing electrocatalytic efficiency. The ZAB assembled with CoNC@NCXS catalyst had a discharge specific capacity of 710 mAh g−1 at a current density of 10 mA cm−2, which was superior to that of the Pt/C&RuO2 catalyst-assembled battery (667 mAh g−1). After running for 150 h, the charge and discharge efficiency of the CoNC@NCXS battery decreased by only 12.8%, which confirmed the excellent stability of the CoNC@NCXS catalyst. The free energy diagrams showed that, CoNC@NCXS has lower energy barriers and higher potential than CoNC in key reaction steps. This study provides a new perspective for the structural design of highly active composite catalysts in energy storage and conversion.

Exploring low barrier quantum tunneling and structural planarity in 3-methylstyrene conformers: Insights from microwave spectroscopy.

The first ground-state rotational spectrum of 3-methylstyrene (3MS) was measured by Fourier transform microwave spectroscopy under supersonic jet-cooled conditions. Transitions were assigned for two conformers: cis-3MS and trans-3MS. In the cis conformer, the vinyl group is oriented toward the methyl group, while in the trans conformer, it is positioned away from the methyl. The energy difference between the two conformers was calculated to be only 2.1cm-1, with the cis conformer having lower energy. Significant tunneling splitting, caused by the low-barrier internal rotation of the methyl group, was observed and analyzed using the XIAM and BELGI-Cs codes. The BELGI results show that the V3 barrier is 30.6688(87) cm-1 for the cis conformer and 11.0388(88) cm-1 for the trans conformer. The experimental rotational and torsional parameters are compared to their density functional theory counterparts. The planarity of the molecular geometry of cis- and trans-3MS is discussed, contributing to the long-standing topic of discussion about the planarity of styrene derivatives.

NH4+-Modulated Cathodic Interfacial Spatial Charge Redistribution for High-Performance Dual-Ion Capacitors

Compared with Zn2+, the current mainly reported charge carrier for zinc hybrid capacitors, small-hydrated-sized and light-weight NH4+ is expected as a better one to mediate cathodic interfacial electrochemical behaviors, yet has not been unraveled. Here we propose an NH4+-modulated cationic solvation strategy to optimize cathodic spatial charge distribution and achieve dynamic Zn2+/NH4+ co-storage for boosting Zinc hybrid capacitors. Owing to the hierarchical cationic solvated structure in hybrid Zn(CF3SO3)2-NH4CF3SO3 electrolyte, high-reactive Zn2+ and small-hydrate-sized NH4(H2O)4+ induce cathodic interfacial Helmholtz plane reconfiguration, thus effectively enhancing the spatial charge density to activate 20% capacity enhancement. Furthermore, cathodic interfacial adsorbed hydrated NH4+ ions afford high-kinetics and ultrastable C‧‧‧H (NH4+) charge storage process due to a much lower desolvation energy barrier compared with heavy and rigid Zn(H2O)62+ (5.81 vs. 14.90eV). Consequently, physical uptake and multielectron redox of Zn2+/NH4+ in carbon cathode enable the zinc capacitor to deliver high capacity (240mAhg-1 at 0.5Ag-1), large-current tolerance (130mAhg-1 at 50Ag-1) and ultralong lifespan (400,000 cycles). This study gives new insights into the design of cathode-electrolyte interfaces toward advanced zinc-based energy storage.

Computational Modeling of Electrocatalysts for CO2 Reduction: Probing the Role of Primary, Secondary, and Outer Coordination Spheres.

ConspectusIn the search for efficient and selective electrocatalysts capable of converting greenhouse gases to value-added products, enzymes found in naturally existing bacteria provide the basis for most approaches toward electrocatalyst design. Ni,Fe-carbon monoxide dehydrogenase (Ni,Fe-CODH) is one such enzyme, with a nickel-iron-sulfur cluster named the C-cluster, where CO2 binds and is converted to CO at high rates near the thermodynamic potential. In this Account, we divide the enzyme's catalytic contributions into three categories based on location and function. We also discuss how computational techniques provide crucial insight into implementing these findings in homogeneous CO2 reduction electrocatalysis design principles. The CO2 binding sites (e.g., Ni and "unique" Fe ion) along with the ligands that support it (e.g., iron-sulfur cluster) form the primary coordination sphere. This is replicated in molecular electrocatalysts via the metal center and ligand framework where the substrate binds. This coordination sphere has a direct impact on the electronic configuration of the catalyst. By computationally modeling a series of Ni and Co complexes with bipyridyl-N-heterocyclic carbene ligand frameworks of varying degrees of planarity, we were able to closely examine how the primary coordination sphere controls the product distribution between CO and H2 for these catalysts. The secondary coordination sphere (SCS) of Ni,Fe-CODH contains residues proximal to the active site pocket that provide hydrogen-bonding stabilizations necessary for the reaction to proceed. Enhancing the SCS when synthesizing new catalysts involves substituting functional groups onto the ligand for direct interaction with the substrate. To analyze the endless possible substitutions, computational techniques are ideal for deciphering the intricacies of substituent effects, as we demonstrated with an array of imidazolium-functionalized Mn and Re bipyridyl tricarbonyl complexes. By examining how the electrostatic interactions between the ligand, substrate, and proton source lowered activation energy barriers, we determined how best to pinpoint the SCS additions. The outer coordination sphere comprises the remaining parts of Ni,Fe-CODH, such as the elaborate protein matrix, solvent interactions, and remote metalloclusters. The challenge in elucidating and replicating the role of the vast protein matrix has understandably led to a localized focus on the primary and secondary coordination spheres. However, certain portions of Ni,Fe-CODH's expansive protein scaffold are suggested to be catalytically relevant despite considerable distance from the active site. Closer studies of these relatively overlooked areas of nature's exceptionally proficient catalysts may be crucial to continually improve upon electrocatalysis protocols. Mechanistic analysis of cobalt phthalocyanines (CoPc) immobilized onto carbon nanotubes (CoPc/CNT) reveals how the active site microenvironment and outer coordination sphere effects unlock the CoPc molecule's previously inaccessible intrinsic catalytic ability to convert CO2 to MeOH. Our research suggests that incorporating the three coordination spheres in a holistic approach may be vital for advancing electrocatalysis toward viability in mitigating climate disruption. Computational methods allow us to closely examine transition states and determine how to minimize key activation energy barriers.

Paired Photoproduction of H2O2 and 3,4-Dihydroisoquinoline over Covalent Pyrene-(Thio)urea Frameworks with Electron Push-Pull Effect.

Pairing photocatalytic 1,2,3,4-tetrahydroisoquinoline semi-dehydrogenation reaction (THIQ-SDR) with two-electron oxygen reduction reaction (2e- ORR) is a green solar to chemical strategy by simultaneously utilizing the photo-excited electrons and holes. However, it is still short of high-efficiency photocatalyst to drive two reactions above. In the present work, crystalline pyrene-thiourea/urea covalent organic frameworks (COF-Py-S and -O) were synthesized and demonstrated as high-performance metal-free photocatalysts. In particular, COF-Py-S exhibited higher 2e- ORR to H2O2 yield rate of ~19 mmol g-1 h-1 under visible light and finally solid H2O2 products (Na2CO3•1.5H2O2) was collected after long-time irradiation. Under natural sunlight conditions, the H2O2 production rate over COF-Py-S further increased to ~51 mmol g-1 h-1, among the best organic photocatalysts. COF-Py-S also showed high THIQ-SDR conversion (~100%) with 3,4-dihydroisoquinoline (DHIQ) selectivity of ~92%. Theoretical calculations reveal stronger electron push-pull effect of COF-Py-S than COF-Py-O, enhancing its photoinduced charge carries, and a four-step 2e- ORR mechanism with thiourea as the active sites has been confirmed as well as the mechanism of THIQ-SDR to DHIQ, featuring lower energy barriers for O2 adsorption and *HOOH desorption over thiourea units. This work provides a paired photosynthesis strategy of H2O2 and DHIQ over high-efficiency pyrene-(thio)urea COF photocatalysts with electron push-pull effect.

Modulation of Co spin state at Co3O4 crystalline-amorphous interfaces for CO oxidation and N2O decomposition

Modulation of electronic spin states in cobalt-based catalysts is an effective strategy for molecule activations. Crystalline-amorphous interfaces often exhibit unique catalytic properties due to disruptions of long-range order and alterations in electronic structure. However, the mechanisms of molecule activation and spin states at interfaces remain elusive. Herein, we present a Co3O4 spinel-based catalyst featuring crystalline-amorphous interfaces. Characterization analyses confirm that tetrahedral Co2+ is selectively etched from bulk spinel, forming amorphous CoO islands on the surface. The resultant symmetry breaking in the coordination field induces a reconstruction of the Co3+3 d orbitals, leading to high-spin states. In CO oxidation, the interface serves as novel active sites with a lower energy barrier, facilitated by lattice oxygen activation. In N2O decomposition, the interface promotes reassociation of dissociated oxygen through quantum spin exchange interactions. This work provides a straightforward approach to modulating the spin state of interfaces and elucidates their role in molecule activations.

Surface Reconstruction of An Integrated CoO‐Co2Mo3O8 electrode Enabling Efficient Ampere‐Level Hydrogen Evolution in Alkaline Water or Seawater

To accelerate the water dissociation in the Volmer step and alleviate the destruction of bubbles to the physical structure of catalysts during the alkaline hydrogen evolution, an integrated electrode of cobalt oxide and cobalt‐molybdenum oxide grown on Ni foam, named CoO‐Co2Mo3O8, is designed. This integrated electrode enhances the catalyst‐substrate interaction confirmed by a micro‐indentation tester, and thus hinders the destruction of the physical structure of catalysts caused by bubbles. Electrochemical testing shows the occurrence of a surface reconstruction of the integrated electrode, and CoO is transformed into Co(OH)2, denoted as Co(OH)2‐Co2Mo3O8. Theoretical calculations determine that Co(OH)2‐Co2Mo3O8 has significantly low activation barrier for water dissociation and presents easy hydroxide desorption, which accelerate the catalytic reaction. Electrochemical experiments show that Co(OH)2‐Co2Mo3O8 exhibits outstanding activity, reaching current density values of −100 and −1000 mA cm−2 with overpotentials only 57.8 and 195.8 mV, respectively. Furthermore, it demonstrates excellent stability at −500 and −1000 mA cm−2 for 200 h. Combined with the previously reported anode, the two‐electrode system also provides the stable operation from 100 to 1000 mA cm−2 for 600 h in alkaline solution, and over 200 h at 500 and 1000 mA cm−2 in alkaline seawater.

Surface Reconstruction of An Integrated CoO-Co2Mo3O8 electrode Enabling Efficient Ampere-Level Hydrogen Evolution in Alkaline Water or Seawater.

To accelerate the water dissociation in the Volmer step and alleviate the destruction of bubbles to the physical structure of catalysts during the alkaline hydrogen evolution, an integrated electrode of cobalt oxide and cobalt-molybdenum oxide grown on Ni foam, named CoO-Co2Mo3O8, is designed. This integrated electrode enhances the catalyst-substrate interaction confirmed by a micro-indentation tester, and thus hinders the destruction of the physical structure of catalysts caused by bubbles. Electrochemical testing shows the occurrence of a surface reconstruction of the integrated electrode, and CoO is transformed into Co(OH)2, denoted as Co(OH)2-Co2Mo3O8. Theoretical calculations determine that Co(OH)2-Co2Mo3O8 has significantly low activation barrier for water dissociation and presents easy hydroxide desorption, which accelerate the catalytic reaction. Electrochemical experiments show that Co(OH)2-Co2Mo3O8 exhibits outstanding activity, reaching current density values of -100 and -1000 mA cm-2 with overpotentials only 57.8 and 195.8 mV, respectively. Furthermore, it demonstrates excellent stability at -500 and -1000 mA cm-2 for 200 h. Combined with the previously reported anode, the two-electrode system also provides the stable operation from 100 to 1000 mA cm-2 for 600 h in alkaline solution, and over 200 h at 500 and 1000 mA cm-2 in alkaline seawater.

Computational Insights Into Corrosion Inhibition Mechanism: Dissociation of Imidazole on Iron Surface.

Corrosion inhibitors are widely used to mitigate safety risks and economic losses in engineering, yet post-adsorption processes remain underexplored. In this study, we employed density functional theory calculations with a periodic model to investigate the dissociation mechanisms of imidazole on the Fe(100) surface. Imidazole was found to adsorb optimally in a parallel orientation, with an adsorption energy of -0.88 eV. We explored two dissociation pathways: CH and NH bond cleavages and found CH dissociation having a lower activation barrier of 0.46 eV. Intriguingly, an alternative indirect route CH dissociation pathway involving a tilted intermediate state was found to be competitive. Both indirect and direct CH dissociation pathways are energetically more favorable than NH cleavage. Molecular dynamics simulations reveal that indirect CH dissociation occurs rapidly. This study proposes an alternative protective mechanism involving dissociated imidazole inhibitors, offering new insights for corrosion inhibitor design.

A Comparative Study on the Structural, Physicochemical, Release, and Antioxidant Properties of Sodium Casein and Gelatin Films Containing Sea Buckthorn Oil

The aim of this study was to compare the effect of increasing concentrations (0, 1, 2, 4%) of sea buckthorn oil (SBO) on the structural, physicochemical, release, and antioxidant properties of glycerol-plasticized sodium casein (NaCAS) and gelatin (GEL) films. Ultrasonic treatment ensured effective homogenization of SBO in both types of emulsions, resulting in yellow-tinted semi-opaque films with relatively low micro-roughness. Generally, GEL films demonstrated lower UV barrier properties and solubility but exhibited higher compactness, crystallinity, transparency, surface hydrophobicity, oxygen barrier performance, strength, and antiradical activity compared to their NaCAS-based counterparts. In a concentration-dependent manner, SBO decreased the solubility and water absorption of the gelatin-based film and enhanced its oxygen permeability. Conversely, SBO improved the water vapor barrier properties of both films in a concentration-independent manner. At the highest SBO concentration, the tensile strength of NaCAS- and GEL-based films decreased by 27% and 20%, respectively, while their antiradical activity increased by 9.3× and 4.3× (based on the time required for the half-neutralization of 2,2-diphenyl-1-picrylhydrazyl radicals). Migration studies showed that at the lowest concentration, SBO was released (into 95% ethanol) approximately 2× faster from the GEL-based film than from the NaCAS film, whereas at higher concentrations, the trend reversed.

Transparent OLED displays for selective bidirectional viewing using ZnO/Yb:Ag cathode with highly smooth and low-barrier surface

Transparent organic light-emitting diode (TrOLED) displays represent cutting-edge technology posed to significantly enhance user experience. This study addresses two pivotal challenges in TrOLED development. Firstly, we focus on the innovation of transparent cathodes, a fundamental component in TrOLEDs, by introducing a ZnO/Yb:Ag cathode. This cathode employs a combination of seed layer and metal doping techniques to achieve a highly uniform surface morphology and a low surface energy barrier. The optimized Yb:Ag cathode on ZnO, with a mere thickness of 15 nm, exhibits remarkable properties: an extremely low surface roughness of 0.52 nm, sheet resistance of 11.6 Ω ϒ−1, an optical transmittance of 86.7% at 510 nm, and tunable work function (here, optimized to be 3.86 eV), ensuring superior electron injection capability. Secondly, we propose a novel TrOLED pixel structure that features selective bidirectional viewing, allowing different types of information to be selectively displayed on each side while preserving overall transparency and minimizing pixel complexity. This design innovation distinguishes itself from conventional TrOLEDs that display images on only one side. The bidirectional TrOLED design not only enhances openness and esthetic appeal but also holds promise for diverse applications across various user environments.

Local Polarization Piezoelectric Electric Field Promoted Water Dissociation for Hydroxyl Radical Generation under Ambient Humidity Condition.

Combining piezocatalysts with mechanical ball milling for dissociating water to generate hydroxyl radicals (·OH) offers unprecedented opportunities for energy conversion and environmental remediation. However, the in-depth insights into the relationship between water and local polarization piezoelectric electric field (LPPEF) are currently lacking, in particularly, the ·OH formation mechanism in ball milling driven piezocatalyst system is not systematically elucidated. To this end, the present work constructs a ball milling driven piezoelectric solid/liquid interface between piezoelectric Pb2B5O9Cl (PBOC) and different contents of water to investigate LPPEF initiated catalytic reaction. Results show that PBOC exhibits an excellent Tetrabromobisphenol A (TBBPA) degradation efficiency with a 68.94 and 12.43 times faster rate constant than traditional SiO2 and BaTiO3, respectively. Under ambient humidity condition, the lower energy barrier of water dissociation (0.23eV) endows ·OH generation more energetically favorable than under the water-oversaturated condition (0.66eV), and trace water magnifies the polarizability of [BO3] and [BO4] units in PBOC to initiate an enhanced LPPEF, thus it enhances the trapping of lone pairs electrons in trace adsorbed water by holes to contribute a higher yield of ·OH. This study constructs a highly correlated field-initiated electron transfer system that provides opportunities for promoting the performance of piezocatalytic materials.

Controllable synthesis of nonlayered high-κ Mn3O4 single-crystal thin films for 2D electronics

Two-dimensional (2D) materials have been identified as promising candidates for future electronic devices. However, high dielectric constant (κ) materials, which can be integrated with 2D semiconductors, are still rare. Here, we report a hydrate-assisted thinning chemical vapor deposition (CVD) technique to grow manganese oxide (Mn3O4) single crystal nanosheets, enabled by a strategy to minimize the substrate lattice mismatch and control the growth kinetics. The material demonstrated a dielectric constant up to 135, an equivalent oxide thickness (EOT) as low as 0.8 nm, and a breakdown field strength (Ebd) exceeding 10 MV/cm. MoS2 field-effect transistors (FETs) integrated with Mn3O4 thin films through mechanical stacking method operate under low voltages (<1 V), achieving a near 108 Ion/Ioff ratio and a subthreshold swing (SS) as low as 84 mV/dec. The MoS2 FET exhibit nearly zero hysteresis (<2 mV/MV cm⁻¹) and a low drain-induced barrier lowering (~20 mV/V). This work further expands the family of 2D high-κ dielectric materials and provides a feasible exploration for the epitaxial growth of single-crystal thin films of non-layered materials.

Integration of p-Type PdPc and n-Type SnZnO into Hybrid Nanofibers Using Simple Chemical Route for Enhancement of Schottky Diode Efficiency

Palladium phthalocyanine (PdPc) and palladium phthalocyanine integrated with tin–zinc oxide (PdPc:SnZnO) were prepared using a simple chemical approach, and their structural and morphological properties were identified using X-ray diffraction, energy dispersive X-ray analysis, scanning electron microscopy, and transmission electron microscopy techniques. The PdPc:SnZnO nanohybrid revealed a polycrystalline structure combining n-type metal oxide SnZnO nanoparticles with p-type organic PdPc molecules. The surface morphology exhibited wrinkled nanofibers decorated with tiny spheres and had a large aspect ratio. The thin film revealed significant optical absorption within the ultraviolet and visible spectra, with narrow band gaps measured at 1.52 eV and 2.60 eV. The electronic characteristics of Al/n-Si/PdPc/Ag and Al/n-Si/PdPc:SnZnO/Ag Schottky diodes were investigated using the current–voltage dependence in both the dark conditions and under illumination. The photodiodes displayed non-ideal behavior with an ideality factor greater than unity. The hybrid diode showed considerably high rectification ratio of 899, quite a low potential barrier, substantial specific photodetectivity, and high enough quantum efficiency, found to be influenced by dopant atoms and the unique topological architecture of the nanohybrid. The capacitance/conductance–voltage dependence measurements revealed the influence of alternative current signals on trapped centers at the interface state, leading to an increase in charge carrier density.

Unraveling the Role of Interfacial Interactions in Electrical Contacts of Atomically Thin Transition-Metal Dichalcogenides.

Van der Waals (vdW) contact has been widely regarded as one of the most potential strategies for exploiting low-resistance metal-semiconductor junctions (MSJs) based on atomically thin transition-metal dichalcogenides (TMDs), but this method is still not efficient due to weak metal-TMD interfacial interactions. Therefore, an understanding of interfacial interactions between metals and TMDs is essential for achieving low-resistance contacts with weak Fermi level pinning (FLP). Herein, we report how the interfacial interactions between metals and TMDs affect the electrical contacts by considering more than 90 MSJs consisting of a semiconducting TMD channel and different types of metal electrodes, including bulk metals, MXenes, and metallic TMDs. We reveal that the vdW contact scheme cannot ensure the formation of low-resistance metal-TMD contacts. The interfacial coupling between metals and TMDs leads to a delicate competition between the FLP and carrier tunneling efficiency, which explains the broad experimental observations in which the weakly coupled van der Waals contacts usually show high contact resistance, while the strongly coupled metal-TMD contacts suffer from strong FLP. Benefiting from the low Schottky barrier and weak FLP, bulk Ag is a promising electrode for n-type MoS2 devices with a contact resistance of 83 Ω μm at a carrier concentration of 5.95 × 1013 cm-2, and 1T'-phase MoS2 and Sc2NO2 are identified as superior contact electrodes for p-type WSe2 devices. This work offers a general rule to exploit high-performance MSJs and clarifies the key role of interfacial coupling in the electrical contacts of TMD-based devices.

Separating nanobubble nucleation for transfer-resistance-free electrocatalysis

Electrocatalytic gas-evolving reactions often result in bubble-covered surfaces, impeding the mass transfer to active sites. Such an issue will be worsened in practical high-current-density conditions and can cause sudden cell failure. Herein, we develop an on-chip microcell-based total-internal-reflection-fluorescence-microscopy to enable operando imaging of bubbles at sub-50 nm and dynamic probing of their nucleation during hydrogen evolution reaction. Using platinum-interfacial metal layer-graphene as model systems, we demonstrate that the strong binding energy between interfacial metal layer and graphene—evidenced by a reduced metal-support distance and enhanced charge transfer—facilitates hydrogen spillover from platinum to the graphene support due to lower energy barriers compared to the platinum-graphene system. This results in the spatial separation of bubble nucleation from the platinum surface, notably enhancing catalytic activity, as demonstrated in both microcell and polymer electrolyte membrane cell experiments. Our findings offer insights into bubble nucleation control and the design of electrocatalytic interfaces with minimized transfer resistance.

Functional Alloy Collector Capable of Sustainable Lithium Compensation for Anode‐Free Batteries by a Controlled Lithium‐Prestorage Technology

AbstractWith higher energy density and reduced cost, anode‐free battery has attracted great attention from both academic and industry. However, the development of anode‐free batteries is hindered by their poor cycle life due to the continuous irreversible lithium (Li) consumption at the anode side. Here, a surface‐functionalized alloy foil, which can gradually release active lithium to the cell upon cycling, used as the collector for anode‐free batteries is proposed. The alloy foil is prestored with a certain amount of active lithium via a simple wet contacting reaction between the metal foil and liquid lithium source reagent. The prestored lithium amount can be precisely controlled by reagent concentration and contact time. When the foil is used as the anode, its alloyed surface demonstrates a low nucleation barrier for lithium deposition and a more uniform deposition behavior. More importantly, the alloy collector can rationally release active lithium to sustainably compensate for the irreversible Li consumption upon the cycling of a full cell, thus greatly prolonging the cycle life of the anode‐free battery by 10 times. Besides, this technique can be extended to diverse metal collectors demonstrating its broad applicability.

P1214 Too Many Couch Potatoes Among Middle-Aged Inflammatory Bowel Disease Patients! Findings From the “BE-FIT-IBD-2” Study on Patient-Reported Physical Activity Levels Examining Their Interactions with IBD-Related Factors and Barriers/Facilitators

Abstract Background Regular physical activity (PA) is desirable, regardless of age, even in patients with chronic conditions such as those with inflammatory bowel disease (IBD), although this issue has been addressed heterogeneously in this setting, with the absence of clear recommendations to follow. This study aimed to assess PA levels in IBD patients, stratifying them into age groups (with a threshold of 50 years), highlighting differences, including barriers/facilitators to PA. Methods The Italian-validated International PA questionnaire (IPAQ) assessed PA levels regarding resting metabolic rate (Met) in minutes/week. Patients were classified as inactive (&amp;lt; 700 Met min/wk), sufficiently active (700-2500 Met min/wk), or active/HEPA (&amp;gt; 2500 Met min/wk) based on the total score computed from the different types of PA intensities. IBD disease activity was evaluated using patient-reported outcomes 2 (PRO-2). Additionally, a questionnaire was administered to identify factors promoting/hindering regular PA in this setting. Results Among the 237 enrolled patients [median age of 43 (30 - 56) years; 149 (62.9%) below the age of 50 and 88 (37.1%) aged at least 50 years], PA rates were found to differ significantly in terms of patients being sufficiently active (55% vs. 39.8%), inactive (39.6% vs. 59.1%), and engaging in health-enhancing PA (5.4% vs. 1.1%) between patients under and at least 50 years old, respectively (P=0.0002). Overall PA levels followed this trend, being higher in younger patients [892 (446.5 - 1439) vs. 545.25 (257 - 1210.47) Met min/wk, P=0.007]. Being at least 50 predicted physical inactivity (β=1.194, OR: 3.302, 95% CI 1.224 - 8.905, P=0.018). A weak negative correlation was found between age and PA total score for intense activities (□□□□= -0.127, p = 0.049). Disease activity did not impact PA levels (p &amp;gt; 0.05). Patients aged at least 50 years perceived IBD as more of a barrier to PA compared to younger individuals (P=0.04). Bowel urgency is a significant barrier, especially in older patients. The significance patients placed on discussing PA with their IBDologist, on a 10-point Likert scale, was not influenced by age group [6 (4 - 8) vs. 5 (3 - 8), P=0.119]. Figures A-P summarize these results. Conclusion Age is an unmodifiable factor that impacts and influences PA levels. Strategies to recover exercise levels in older IBD patients should be encouraged. References Gravina AG, Pellegrino R, Durante T, et al. Inflammatory bowel diseases patients suffer from significant low levels and barriers to physical activity: The "BE-FIT-IBD" study. World J Gastroenterol. 2023;29(41):5668-5682. doi:10.3748/wjg.v29.i41.56682. Gravina AG, Pellegrino R, Palladino G, et al. Profiling the patient with inflammatory bowel disease in the relationship between physical activity and partner/social network status: A post hoc patient-tailored analysis of the "BE-FIT-IBD" study. Gastroenterol Hepatol. Published online May 8, 2024:S0210-5705(24)00161-4. doi:10.1016/j.gastrohep.2024.5022033. Craig CL, Marshall AL, Sjöström M, et al. International physical activity questionnaire: 12-country reliability and validity. Med Sci Sports Exerc. 2003;35(8):1381-1395. doi:10.1249/01.MSS.0000078924.61453.FB

Metallic Sliding Ferroelectricity in Trilayer Penta‐NiN2

AbstractThe experimental observation of metallic ferroelectricity has challenged the traditional understanding in recent years, as metallicity and ferroelectricity are historically considered mutually exclusive. This breakthrough has sparked significant interest in this field. However, the coexistence of metallicity and sliding ferroelectricity in 2D pentagonal materials has not been reported yet. Here, this is theoretically studied that the sliding ferroelectricity in metallic trilayer penta‐NiN2. By scanning the configuration space of stacking patterns, a pair of polarized configurations is identified with strong out‐of‐plane ferroelectric polarization of ± 5.39 × 10−13 C m−1 and a low polarization switching barrier of 14.33 meV/atom together with a non‐polarized configuration as the intermediate state for the ferroelectric transition. It is also found that there are substantial changes in the second harmonic generation of the stable configurations that would facilitate experimental observation. This work demonstrates the potential of pentagonal sheets as promising metallic sliding ferroelectrics, which would significantly expand the family of sliding ferroelectric materials.