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At least 1,261 records · Page 70

Comparing Intrinsic Catalytic Activity and Practical Performance of Ni- and Pt-Based Alkaline Anion Exchange Membrane Water Electrolyzer Cathodes

The stringent cost and performance requirements of renewable hydrogen production systems dictate that electrolyzers benefit from the use of nonprecious catalysts only if they deliver the same level of activity and durability as their precious metal counterparts. Here we report on recent work to understand interrelationships between the intrinsic activity of Ni- and Pt-based electrolyzer cathode catalysts and their performance in zero-gap alkaline water electrolyzer assemblies. Our results suggest that nanoparticulate Ni–Mo exhibits HER activity that is roughly 10-fold lower than Pt–Ru on the basis of turnover frequency under low (≤100 mV) polarization conditions. We further found that the HER activity of Ni–Mo/C cathodes is inhibited by aryl piperidinium anionexchange ionomers bearing bicarbonate counter-anions. After addressing this poisoning effect, we produced electrolyzer assemblies based on Ni–Mo/C cathodes that delivered indistinguishable current density vs cell potential relationships compared to otherwise identical assemblies with Pt–Ru cathodes. This result indicates that the contribution of the cathode to the total cell polarization is small, even for the less active Ni–Mo/C catalyst, and further implies that Pt-based cathodes can indeed be replaced by nonprecious alternatives with no loss in performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synchronized Breathing in Anion-Derived Interphases

Anion-derived interphases are crucial for extending the cycle life of lithium metal batteries. While their benefits are often attributed to crystalline inorganic species like LiF and Li 2 O, the role of amorphous inorganic species and the interplay between the anode-electrolyte interphase (SEI) and the cathode-electrolyte interphase (CEI) remain largely unexplored. Here, in this study, we examine two model electrolyte systems─one with solvent-derived interphases and the other with anion-derived interphases─using advanced X-ray scattering and spectroscopy techniques. Our findings reveal that anion-derived interphases contain substantial amounts of amorphous inorganic species, leading to a unique synchronization of "breathing" between SEI and CEI. During charging, the SEI grows while the CEI shrinks; during discharging, these roles reverse. This distinctive interfacial behavior originates from the competition of deposition and dissolution of amorphous inorganics during cycling. The study highlights the unique role of amorphous inorganics in anion-derived interphases, providing new insights into improving battery performance and durability.

25 ENERGY STORAGE↗

Electrolyte Immersion Increases Photoconductivity in a Model Polymer Photocathode

Immersing polymer solar cells in aqueous electrolyte for photoelectrochemical (PEC) hydrogen production is likely to cause photophysical changes that could present both challenges and opportunities for engineering functional and durable devices. Herein we study the bulk heterojunction blend poly(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene-2,6-diyl)-alt-(2-(((2-ethylhexyl)oxy)carbonyl)-3-fluorothieno[3,4-b]thiophene-4,6-diyl):poly(N,N'-di(2-octyldodecyl)naphthalene-1,8:4,5-bis(dicarboximide)-2,6-diyl)-alt-(2,2-bithiophene-5,5'-diyl) (PTB7-Th:N2200) excited-state dynamics in electrolyte from femtosecond to millisecond time scales using pump-probe microwave conductivity and absorption spectroscopy. While the blend swells very little, electrolyte exposure increases the microwave-frequency mobility and possibly the yield of photogenerated charges while also decreasing crystallinity. These results indicate an enhancement in key performance metrics, implying that any limitations on the performance of PEC test devices do not arise from active layer-electrolyte interactions. For the PTB7-Th:N2200 blend or similar photocathode systems, our results indicate that improving the interfacial kinetics and/or the carrier lifetime should be prioritized, not protecting the active layer from the electrolyte. Since this observation may not be universal to all polymer systems, future research should focus on identifying their limiting photophysical processes. electrolyte.

14 SOLAR ENERGY↗

Toward Fullerene-Free PIN Perovskite Solar Cells

We highlight opportunities for a transformative shift in perovskite solar cell design by expanding electron transport layers (ETLs) beyond fullerenes. Fullerenes have known limitations, including constraints on open-circuit voltage, stability, and mechanical integrity. Recently, fullerene-free p-i-n cells with power conversion efficiencies exceeding 25% have been demonstrated via both naphthalene diimide-SnO x bilayers and nonfullerene acceptor-based ETLs. Despite successes, fullerenes remain the de facto ETLs for perovskites. Drawing lessons from organic photovoltaics, where it took decades to transition from fullerenes to more broadly available and efficient materials, we explore pathways to accelerate the development and adoption of fullerene-free ETLs. This requires understanding the similarities and differences between organic and perovskite solar cells, which will necessitate carefully designing fullerene replacements with both, high efficiency and also, critically, durability under operation. Here, we incorporate literature data to facilitate comparisons, and independently conduct fracture energy measurements for alternative ETL configurations to motivate their adoption.

14 SOLAR ENERGY↗

Hole-Transport Layer for High Current Density and Stability of Sn-Pb Perovskites and All-Perovskite Tandem Solar Cells

Sn-Pb perovskites are essential for achieving efficient single-junction solar cells and all-perovskite tandem solar cells (APTSCs). Although Sn oxidation and defective surfaces were once major limitations, recent advances in intrinsic material quality have largely mitigated these issues. As a result, the HTL-related interface is now regarded as the primary bottleneck for device performance. To address the intrinsic drawbacks of PEDOT:PSS, chemical surface modification and additive strategies have been widely applied, and alternative HTLs, like polymeric, inorganic, or small-molecule HTLs, have also gained attention. These approaches offer improved energy-level alignment, high transparency, and enhanced chemical durability, leading to higher short-circuit current density and longer operational lifetime in both single-junction and tandem devices. In this Perspective, we highlight the key criteria and practical effects of HTL materials suitable for Sn-Pb perovskites.

14 SOLAR ENERGY↗

Chemical and Structural Insights into Solid Electrolyte Interphase Evolution for Sodium Metal Electrodes

The solid electrolyte interphase (SEI) critically governs the reversibility of sodium metal batteries, through dynamically mediating ion transport and interfacial reactions. However, its kinetic evolution under operating conditions, and how it influences interfacial stability, remains poorly understood. Here, in this study, we reveal that the SEI undergoes coupled chemical and mechanical changes during sodium plating and stripping, leading to spatial and temporal heterogeneity that drives interfacial degradation. Synchrotron operando grazing-incidence wide-angle X-ray scattering and soft X-ray absorption spectroscopy capture the sequential formation and dissolution of inorganic SEI phases (NaF, NaH, NaOH, Na 2 PO 3 F), accompanied by depth-dependent alterations in organic SEI components. Mesoscale modeling connects this evolving SEI heterogeneity to localized current density fluctuations and stress accumulation at the Na interface, identifying pathways to electrically isolated sodium formation. These findings show that SEI instability fundamentally limits reversibility in sodium metal batteries, and that controlling SEI chemistry–mechanics coupling is essential to achieving its durability.

36 MATERIALS SCIENCE↗

Eutectic Processing of Semiconductor Colloidal Nanocrystals for Energy Applications

Colloidal semiconductor nanocrystals (NCs) offer a costeffective platform for light-energy conversion in X-ray scintillators, photovoltaics, lasers, and display technologies. Yet, device-relevant NCs often require complex heterostructured compositions, where lattice imperfections compromise the efficiency and stability of photoconversion processes. Here, we show that a simple synthetic detour through a eutectic state of II−VI semiconductor NCs (e.g., CdSe, ZnSe) with halide salts (e.g., CdCl 2 , ZnCl 2 ) overcomes this limitation by melting and reconstructing NC lattices into defect-free alloyed and core/shell architectures. Applied to ternary CdSeTe NCs, this process produces downconverters with record brightness and minimal line widths, delivering a 3-fold increase in film-side external quantum efficiency of commercial CdTe photovoltaic modules (First Solar Inc.). Meanwhile, eutectic processing of CdSe-based core/shell emitters yields an 8-fold enhancement in their photoluminescence stability under backlight operation, addressing the reliability bottleneck for display technologies. Together, these findings establish eutectic NC processing as a scalable route to efficient, durable photoconversion materials for energy applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Mitigating Hydrogen-Induced Degradation of Iridium Anodes in Proton Exchange Membrane Water Electrolyzers

One promising method for reducing precious metal usage in proton exchange membrane water electrolysis is lowering iridium (Ir) loading at the anode. However, low-loading Ir catalysts often suffer from poor stability under high current densities. In this study, hydrogen (H2) crossover from the cathode to the anode is identified as a key degradation pathway. Temperature-programmed reduction confirms the reduction of IrO2 at 80 °C in a hydrogen environment, highlighting the vulnerability of IrO2-based catalysts to H2 exposure. To mitigate this effect, palladium (Pd) is introduced as an anode additive, acting as an H2 oxidation catalyst and mitigating IrO2 reduction. This protective role is verified by inductively coupled plasma optical emission spectroscopy and in situ X-ray absorption spectroscopy, showing significantly suppressed Ir dissolution at 80 °C under H2 flow when an O-covered Pd surface is present at oxygen evolution reaction potentials. Results from the current study identify a new strategy in improving activity and durability of catalysts in electrolyzers.

58 GEOSCIENCES↗

CeO 2 Promoted CuO/MgO-Al 2 O 3 Catalyst with Enhanced Activity and Water-Resistance for CO Oxidation

Copper (Cu)-based catalysts have emerged as cost-effective and sustainable alternatives to noble metal systems (e.g., Pt, Pd) for catalytic CO oxidation. However, their practical application is hindered by insufficient low-temperature activity and rapid deactivation under wet conditions containing moisture. To address these challenges, this work introduces CeO 2 -modified CuO/MgO-Al 2 O 3 (Cu-Ce/MA) catalysts, strategically designed to enhance the catalytic performance and water resistance simultaneously. These catalytic materials were evaluated for CO oxidation under both dry and humid conditions, revealing that CeO 2 modification significantly improves the low-temperature activity. Specifically, the optimal catalyst, Cu-30Ce/MA, achieved a 50% CO conversion temperature (T 50 ) of 151 °C, a marked reduction from 218 °C on Cu/MA reference catalyst. Furthermore, the water resistance improves in a CeO 2 content-dependent manner, with higher CeO 2 loadings imparting greater stability in humid environments. Detailed characterizations demonstrate that CeO 2 promotes the dispersion of CuO and stabilizes Cu sites, while also enhancing the low-temperature reducibility and CO adsorption capacity. Crucially, CeO 2 modification suppresses the competitive H 2 O adsorption, mitigating water-induced deactivation. These synergistic effects collectively rationalize the superior activity and durability of Cu-Ce/MA catalysts. By elucidating the dual role of CeO 2 in optimizing Cu-based systems, this study advances the rational design of cost-effective catalysts for real-world CO emission control, particularly under water-rich industrial conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Enhancing Resource Recovery through Electro-Assisted Regeneration of an Ammonia-Selective Cation Exchange Resin

Ammonia-selective adsorbents can manage reactive nitrogen in the environment and promote a circular nutrient economy. Weak acid cation exchangers loaded with zinc exhibit high ammonia selectivity but face two implementation barriers: the stability of the zinc–carboxylate bond in complex wastewaters and energy- and logistics-intensive adsorbent regeneration with acidic solutions. In this paper, we examined the stability of zinc–carboxylate bonds in varying solutions (pure ammonium solution, synthetic urine, and real urine) and during electro-assisted regeneration. For electrochemical regeneration, both electrolyte concentration and current density influenced the trade-off between ammonia regeneration and zinc elution. Using 10 mM K 2 SO 4 anolyte at a 0.08 mA/cm 2 current density, we achieved 4% zinc elution and 61% ammonia regeneration. In contrast, using 100 mM K 2 SO 4 at 4.96 mA/cm 2 improved the regeneration efficiency to 97% but eluted 60% of zinc. We found that electrolyte concentration was the key factor influencing the regeneration efficiency of the NH 3 -selective adsorbents. Due to prevalent zinc elution, we designed an in situ procedure for reforming the zinc–carboxylate bond and achieved similar adsorption densities between pre- and post-regenerated resins, thus enabling multiple cycle resin use. Ultimately, this study advances understanding of ammonia-selective resins that can facilitate high-purity, selective, and durable recovery of nutrients from waste streams.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chemical Recycling of Carbon Fiber-Reinforced Nylon Composites

Nylon-based fiber-reinforced composites are widely used in various sectors due to their strength, durability, and lightweight properties. Despite their widespread use, recycling these composites is difficult due to the inability to separate fibers and thermal instability of nylon at high temperatures. Consequently, most nylon composites are landfilled, leading to significant economic loss. Current fiber recovery methods (i.e., pyrolysis) are energetically inefficient and preclude recovery of the matrix. Dissolution methods, such as using hexafluoroisopropanol (HFIP), allow recovery of polymer and fiber but are economically taxing and require extensive safety infrastructure. Herein we report tailored glycolysis of nylon-6 composites, resulting in separated constituent fibers and nylon-6 oligomers. Deconstruction kinetics reveal nylon’s molecular weight reductions from 32,600 to 2000 g/mol, while SEM and tensile testing confirm recovered fiber integrity. In conclusion, this approach offers a pathway to reclaim high-value materials from nylon composites, providing a strategy for the chemical recycling of fiber-reinforced composites.

Zheng, Jackie [Univ. of Tennessee, Knoxville, TN (↗

Enzymatic Nylon Deconstruction: Enzyme Discovery, Engineering, and Opportunities

Nylons are widely used synthetic polyamides valued for their strength, versatility, and durability across diverse applications. However, their petrochemical origin and energy-intensive production underscore the need for efficient, circular solutions. Conventional recycling methods remain limited by incomplete recovery, material degradation, and costly sorting requirements. Enzymatic depolymerization offers a selective, low-energy alternative capable of processing mixed waste streams under mild conditions. While significant progress has been achieved for polyesters, enzymatic degradation of polyamides is still at an early stage. The discovery of nylon hydrolases demonstrated the potential of biological systems to evolve catalysts for synthetic polyamides, yet reported depolymerization yields remain low. These limitations reflect both the structural complexity of nylons and the need for improved enzyme discovery and engineering. In conclusion, this review highlights recent advances, key challenges, and future directions for enzymatic nylon recycling, outlining its potential role enabling mixed polymer waste to be used as a green feedstock for remanufacturing.

Amides↗

Scalable Polymeric Few-Nanometer Organosilica Membranes with Hydrothermal Stability for Selective Hydrogen Separation

Nanoporous silica membranes exhibit excellent H 2 /CO 2 separation properties for sustainable H 2 production and CO 2 capture but are prepared via complicated thermal processes above 400 °C, which prevent their scalable production at a low cost. Here, we demonstrate the rapid fabrication (within 2 min) of ultrathin silica-like membranes (~3 nm) via an oxygen plasma treatment of polydimethylsiloxane-based thin-film composite membranes at 20 °C. The resulting organosilica membranes unexpectedly exhibit H2 permeance of 280-930 GPU (1 GPU = 3.347 x 10 -10 mol m -2 s -1 Pa -1 ) and H2/CO2 selectivity of 93-32 at 200 °C, far surpassing state-of-the-art membranes and Robeson’s upper bound for H 2 /CO 2 separation. When challenged with a 3 d simulated syngas test containing water vapor at 200 °C and a 340 d stability test, the membrane shows durable separation performance and excellent hydrothermal stability. The robust H 2 /CO 2 separation properties coupled with excellent scalability demonstrate the great potential of these organosilica membranes for economic H 2 production with minimal carbon emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Conformal PEDOT Coating Enables Ultra-High-Voltage and High-Temperature Operation for Single-Crystal Ni-Rich Cathodes

Single-crystal Ni-rich Li[Ni x Mn y Co 1-x-y ]O 2 (SC-NMC) cathodes represent a promising approach to mitigate the cracking issue of conventional polycrystalline cathodes. However, many reported SC-NMC cathodes still suffer from unsatisfactory cycling stability, particularly under high charge cutoff voltage and/or elevated temperature. Herein, we report an ultraconformal and durable poly(3,4-ethylenedioxythiophene) (PEDOT) coating for SC-NMC cathodes using an oxidative chemical vapor deposition (oCVD) technique, which significantly improves their high-voltage (4.6 V) and high-temperature operation resiliency. The PEDOT coated SC LiNi 0.83 Mn 0.1 Co 0.07 O 2 (SC-NMC83) delivers an impressive capacity retention rate of 96.7% and 89.5% after 100 and 200 cycles, respectively. Significantly, even after calendar aging at 45 degrees C and 4.6 V, the coated cathode can still retain 85.3% (in comparison with 59.6% for the bare one) of the initial capacity after 100 cycles at a 0.5 C rate. Synchrotron X-ray experiments and interface characterization collectively reveal that the conformal PEDOT coating not only effectively stabilizes the crystallographic structure and maintains the integrity of the particles but also significantly suppresses the electrolyte's corrosion, resulting in improved electrochemical/thermal stability. Our findings highlight the promise of an oCVD PEDOT coating for single-crystal Ni-rich cathodes to meet the grand challenge of high-energy batteries under extreme conditions.

25 ENERGY STORAGE↗

Surface Self-Diffusion Induced Sintering of Nanoparticles

Despite the critical role of sintering phenomena in constraining the long-term durability of nanosized particles, a clear understanding of nanoparticle sintering has remained elusive due to the challenges in atomically tracking the neck initiation and discerning different mechanisms. Through the integration of in situ transmission electron microscopy and atomistic modeling, this study uncovers the atomic dynamics governing the neck initiation of Pt–Fe nanoparticles via a surface self-diffusion process, allowing for coalescence without significant particle movement. Real-time imaging reveals that thermally activated surface morphology changes in individual nanoparticles induce significant surface self-diffusion. Further, the kinetic entrapment of self-diffusing atoms in the gaps between closely spaced nanoparticles leads to the nucleation and growth of atomic layers for neck formation. This surface self-diffusion-driven sintering process is activated at a relatively lower temperature compared to the classic Ostwald ripening and particle migration and coalescence processes. The fundamental insights have practical implications for manipulating the morphology, size distribution, and stability of nanostructures by leveraging surface self-diffusion processes.

36 MATERIALS SCIENCE↗

Hierarchical Biogenic-Based Thermal Insulation Foam

Biogenic-based foam, renowned for its sustainable and eco-friendly properties, is emerging as a promising thermal insulating material with the potential to significantly enhance energy efficiency and sustainability in building applications. However, its relatively high thermal conductivity, large-pore configurations, and energy-intensive manufacturing processes hinder its widespread use. Here, we report on the scalable, one-pot synthesis of biogenic foams achieved by integrating recycled paper pulp and in situ nanoporous silica formation, resulting in a hierarchical structure comprising both micropores and nanopores. Ambient solvent-exchange drying can preserve the pore structure by reducing the capillary forces during the drying process. The resulting flame-retardant and hydrophobic foam exhibits low density (0.110 g/cm 3 ), ideal porosity (70.69%), excellent thermal conductivity (0.033 W/(m·K)), and impressive compressive strength (1.48 MPa at 80% strain). Furthermore, this recyclable biogenic foam, with its hierarchical pore structure and environmental durability, shows great potential for energy-efficient building applications.

36 MATERIALS SCIENCE↗

Revealing Sintering Kinetics of MoS 2 -Supported Metal Nanocatalysts in Atmospheric Gas Environments via Operando Transmission Electron Microscopy

The decoration of two-dimensional (2D) substrates with nanoparticles (NPs) serve as heterostructures for various catalysis applications. Deep understanding of catalyst degradation mechanisms during service conditions is crucial to improve the catalyst durability. In this work, we studied the sintering behavior of Pt and bimetallic Au-core Pt-shell (Au@Pt core–shell) NPs on MoS 2 supports at high temperatures under vacuum, nitrogen (N 2 ), hydrogen (H 2 ), and air environments by in situ gas-cell transmission electron microscopy (TEM). The key observations are summarized as effect of environment: while particle migration and coalescence (PMC) was the main mechanism that led to Pt and Au@Pt NPs degradation under vacuum, N 2 , and H 2 environments, the degradation of MoS 2 substrate was prominent under exposure to air at high temperatures. Pt NPs were less stable in H 2 environment when compared with the Pt NPs under vacuum or N 2 , due to Pt–H interactions that weakened the adhesion of Pt on MoS 2 . Effect of NP composition: under H 2 , the stability of Au@Pt NPs was higher in comparison to Pt NPs. This is because H 2 promotes the alloying of Pt–Au, thus reducing the number of Pt at the surface (reducing H 2 interactions) and increasing Pt atoms in contact with MoS 2 . Effect of NP size: The alloying effect promoted by H 2 was more pronounced in small size Au@Pt NPs resulting in their higher sintering resistance in comparison to large size Au@Pt NPs and similar size Pt NPs. The present work provides key insights into the parameters affecting the catalyst degradation mechanisms on 2D supports.

2D materials↗

Mitigating Damage to Hybrid Perovskites Using Pulsed-Beam TEM

Using a pulsed-beam transmission electron microscope, we discover a reduction in damage to methylammonium lead iodide (MAPbI3) as compared to conventional beams delivered at the same dose rates. For rates as low as 0.001 e·Å –2 ·s –1 , we find up to a 17% reduction in damage at a total dose of 10 e·Å –2 . We systematically study the effects of number of electrons in each pulse and the duration between pulse arrival. Damage increases for both, though the number of electrons per pulse has a larger effect. A crossover is identified, where a pulsed beam causes more damage than a conventional one. Although qualitatively similar to previous findings, the degree to which damage is reduced in MAPbI3 is less than that observed for other materials (e.g., C36H74), supporting the hypothesis that the effects are material- and damage-mechanism-dependent. Despite this, the observation here of damage reduction for relatively large electron packets (up to 200 electrons per pulse) suggests that MAPbI3 is in fact less susceptible to irradiation than C36H74, which may be related to reported self-healing effects. This work provides insights into damage processes and durability in hybrid perovskites and also illustrates the viability of using pulsed-beam TEM to explore the associated molecular-level routes to degradation, analogous to laser-accelerated energetic pulsed electron beams and the study of damage to biomolecules, cells, and tissues in radiobiology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗