Surface Reactivity Research Articles

Amphichdiral enhancement on singlet oxygen generation and stable thallium immobilization using iron-driven copper oxide

Thallium (Tl) as a prominent priority contaminant in aquatic environment necessitates rigorous regulation. However, limited horizon devotes the impact of selective oxidation on the process of thallium purification. In this study, selective active radical of singlet oxygen (1O2) was continually generated for Tl(Ⅰ) oxidation accomplished with efficient Tl(Ⅲ) immobilization using iron-driven copper oxide (CuFe)/peroxymonosulfate (PMS). Fe-doping changed the active center of electronic structure for enhancing the catalytic and adsorptive reactivities, and installed magnetism for solid-liquid separation. Rapid reaction rate (0.253 min−1) coupled with vigorous elimination efficiency (98.32%) relied on electrostatic attraction, surface complexation, and H-bond interaction. EPR and XPS analyses demonstrated that the synergistic effects of ≡ Cu(Ⅰ)/≡Cu(Ⅱ) and ≡ Fe(Ⅲ)/≡Fe(Ⅱ) redounded to the sustained generation of 1O2 through the pathway of PMS → •O2− → 1O2, and 1O2 exploited an advantage to selectively oxidize Tl(Ⅰ) to Tl(Ⅲ). 3D isosurface cubic charts revealed that the immobilizing ability of Tl(Ⅲ) hydrate for CuFe was notably superior to that of Tl(Ⅲ) hydrate for CuO and Tl(Ⅰ) hydrate for CuO/CuFe, which further attested surface reactivity promoted stable immobilization form. This work develops the continuous generation of 1O2 and stable immobilization with the goal of efficiently cleansing Tl-containing wastewater.

Improving the mechanical properties of heat-treated wood bonding interphase via plasma treatment

Plasma treatment is an eco-friendly and effective way to improve the chemical reactivity of wood surface. This study explores the improvemnet of bonding properties of heat-treated wood for outdoor construction applications through plasma treatment. In this work, the low temperature atmospheric barrier discharge (DBD) plasma was used to modify the surface of heat-treated wood, and then phenol-formaldehyde (PF) resin adhesive and modified wood were applied to prepare bonded wood. The in-situ chemical structure and mechanical properties of the bonding interphase were characterized by Raman spectrum, nanoindentation and digital image correlation technology (DIC) to indicate the effect of DBD modification on the bonding properties of heat-treated wood. Results showed that after plasma treatment, the hydrophilic functional groups in the cell wall were increased and the PF adhesive molecules had chemical interaction with the cell wall. The elastic modulus (Er) and hardness (H) of wood cell wall gradually decreased along the bonding interphase towards wood with the decrease of PF penetration depth, which resulted in the reduction of the mechanical properties difference between the cell wall and PF adhesive at the bonding interphase. As a result, the shear strain was distributed homogeneously due to the effective stress transmission more at the bonding interphase. The shear strength of the control bonded wood decreased by about 35 % after heat treatment at 215 °C for 2 h, while the shear strength of heat-treated wood was increased by up to 34 % after plasma treatment.

Two-stage feature selection for machine learning-aided DFT-based surface reactivity study on single-atom alloys

This paper presents a feature-centric strategy for predicting adsorption energies of key CO2 reduction reaction (CO2RR) adsorbates, CO and H species, utilizing density functional theory-based calculations for eight adsorption sites and considering alloying effects of nine transition metals at single-atom concentrations. Here, we explore a class of materials consisting of a majority host metal where individual atoms of a different element are dispersed called single-atom alloys (SAA). A total of eight feature selection methods are assessed within Gradient Boosting Regression and Linear Regression models. This study proposes a practical and effective two-stage approach that narrows down the initial 86 features to subsets of 10 and 7 for CO and H adsorption energy predictions, respectively, with the arithmetic mean of valence electrons (VE-am) feature consistently emerging as highly influential, validated through permutation and Shapley additive explanations-based feature importance analyses. The models exhibit robust performance on unseen data, indicating their generalization capability. The findings emphasize VE-am as a potential key machine learning feature for CO2RR on SAA surfaces and underline the effectiveness of the feature-centric approach in understanding feature impacts in machine learning models for CO2RR on SAA systems. Additionally, while other features based on structural, electronic and elemental properties may not individually impact the model significantly, their collective contribution plays a vital role in achieving more accurate adsorption energy predictions.

A Hydridoaluminate Additive Producing a Protective Coating on Ni‐Rich Cathode Materials in Lithium‐Ion Batteries

AbstractTo enhance the energy density of Li‐ion batteries, high‐capacity and high‐voltage cathode materials are needed. Recently, Ni‐rich layered oxides have attracted attention as they can offer ≈200 mAh g−1 when cycled up to 4.3 V. However, cycling these materials in their full capacity range often leads to excessive reactivity with the electrolyte, resulting in particle cracking, transition metal dissolution, and oxygen loss. In this study, the use of lithium hydridoaluminates as electrolyte additives is explored for lithium‐ion batteries based on nickel‐rich cathode materials. Being mild reducing agents, these additives act as HF scavengers, avoiding transition metal dissolution from the cathode. Additionally, their oxidation results in the formation of an Al‐rich protective layer on the cathode, which dampens the surface reactivity, preventing surface reconstruction and impedance build‐up. This study further stresses the important role of the cathode‐electrolyte interface phenomena on the capacity degradation of Ni‐rich cathode materials and provides a novel avenue for controlling this reactivity, thus extending their cycling life.

Influence of Water Radiolysis on the Passive Properties of 316L-Stainless Steel.

This work aims to study the effect of radiolytic species induced by water radiolysis on the passive behavior of 316L stainless steel. For this purpose, the stainless steel/neutral and aerated 0.02 M Na2SO4, electrolyte solution interface was irradiated with proton beams. A wide range of energies between 2 and 16 MeV was selected, varying the maximum of the energy deposition between 0.5 and 122 μm in water from the interface. The irradiation experiments were performed at the CEMHTI cyclotron in Orléans and the 4 MV Van de Graaff accelerator at IP2I in Lyon (France). A dedicated irradiation device implemented with a 3-electrode cell dedicated to perform electrochemical measurements allows to measure the surface reactivity of the stainless steel as a function of the irradiation conditions. Results show that whatever the beam energy, the corrosion potential remains unchanged. It indicates that the very short-lived, highly reactive radiolytic species drive the corrosion potential and not only the recombination products such H2O2 or H2. The stainless steel remains in the passive state whatever the irradiation conditions. However, it is shown that, during irradiation, the passive film is less protective. This evolution is attributed to radiolysis of bound water molecules in the passive film.

Advances on Single‐Atom‐Based Dual‐Site Photocatalysts: Fundamentals, Mechanisms, and Applications

Single‐atom catalysts (SACs) have emerged as leading‐edge research in the field of photocatalysis due to outstanding photocatalytic performance, maximum atomic utilization efficiency, and well‐defined catalytic active sites. However, the singular functionality of active sites in SACs restricts their applications in complex redox reactions involving multiple intermediates and reaction pathways. To circumvent this limitation, a second site comprising single atoms (SA), alloys, clusters, or nanoparticles is proposed to establish SA‐based dual‐site photocatalysts (SA DSPs). While maintaining 100% atomic utilization, the second site and site–site collaboration endow SA DSPs with superior photocatalytic activities to surpass those of SACs. In this review, the latest investigations on SA DSPs featuring diverse compositions, electronic and geometric configurations, site–site collaboration, and metal–support interactions are summarized. Thereafter, the mechanisms underlying enhanced photocatalytic activities are elucidated regarding the roles of the dual sites in charge‐carrier dynamics and surface reactivity. Furthermore, the state‐of‐the‐art applications in photocatalytic hydrogen evolution, CO2 reduction, and methane oxidation, etc., over SA DSPs are discussed. It is anticipated that this review will offer insights into precise control and design of dual sites in photocatalysts, thereby advancing photocatalysis toward commercial viability.

Non-Invasive Multi-Gas Detection Enabled by Cu-CuO/PEDOT Microneedle Sensor.

Metal-oxide-based gas sensors are extensively utilized across various domains due to their cost-effectiveness, facile fabrication, and compatibility with microelectronic technologies. The copper (Cu)-based multifunctional polymer-enhanced sensor (CuMPES) represents a notably tailored design for non-invasive environmental monitoring, particularly for detecting diverse gases with a low concentration. In this investigation, the Cu-CuO/PEDOT nanocomposite was synthesized via a straightforward chemical oxidation and vapor-phase polymerization. Comprehensive characterizations employing X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), X-ray diffraction (XRD), and micro Raman elucidated the composition, morphology, and crystal structure of this nanocomposite. Gas-sensing assessments of this CuMPES based on Cu-CuO/PEDOT revealed that the response current of the microneedle-type CuMPES surpassed that of the pure Cu microsensor by nearly threefold. The electrical conductivity and surface reactivity are enhanced by poly (3,4-ethylenedioxythiophene) (PEDOT) polymerized on the CuO-coated surface, resulting in an enhanced sensor performance with an ultra-fast response/recovery of 0.3/0.5 s.

A novel activation method for regulating surface characteristics and flotation performance of smithsonite: XPS, SEM-EDS, AFM, ToF-SIMS and FT-IR studies

Smithsonite is a typical zinc oxide mineral, and the flotation index is not ideal for the recovery of smithsonite via sulfidization–xanthate flotation. In this study, Pb2+ was used as an activator for the stepwise activation of smithsonite in a sulfidization–xanthate flotation system. Micro-flotation tests and various surface analytical assays were employed to investigate the effects of Pb2+ stepwise activation on the flotation behavior and surface properties of smithsonite. The micro-flotation tests revealed that the flotation recovery of smithsonite reached 90.26 % after the stepwise activation of Pb2+ at an appropriate concentration. X-ray photoelectron spectroscopy, scanning electron microscopy-energy-dispersive X-ray spectroscopy, atomic force microscopy, and time-of-flight secondary ion mass spectrometry indicated that abundant active sites of Pb components appeared on the smithsonite surface after Pb2+ stepwise activation, which promoted the adsorption of S ions on the smithsonite surface. The increase in the proportion of the PbS component after sulfidization effectively enhanced the reaction activity of the mineral surface. Fourier-transform infrared spectroscopy and contact angle measurements showed that xanthate could be stably adsorbed on the smithsonite surface after Pb2+ stepwise activation, thereby enhancing the surface hydrophobicity and flotation behavior of smithsonite. Therefore, Pb2+ stepwise activation can promote sulfidization on the smithsonite surface, improve the reactivity and hydrophobicity of the mineral surface, and substantially increase the flotation index of smithsonite.

Simultaneously improving interfacial adhesion and toughness of carbon fiber reinforced epoxy composites by grafting polyethyleneimine on the carbon fiber surface to construct a rigid‐flexible interface

AbstractChemical grafting is commonly employed to functionalize carbon fiber (CF) surface to enhance the interfacial properties of CF reinforced polymer composites (CFRP) by forming a robust interface. However, an overly rigid interface layer can result in relatively poor interface toughness. To balance interfacial strength and toughness, this paper proposes an effective method to simultaneously strengthen and toughen the interface of CF/epoxy composites by grafting branched polyethyleneimine (PEI) on CF surface using hexachlorophosphazene (HCCP) as active intermediate, which features a rigid ring structure and six active P‐Cl groups. The introduction of PEI provided a large number of amine and imine groups on CF surfaces, which were contributive to improving surface wettability and reactivity of CF, thus resulting in strong chemical bonding between CF and epoxy matrix. Additionally, the long and flexible molecular skeleton of PEI constructed a rigid‐flexible composite interface, which could effectively reduce stress concentration and absorb impact energy. After surface modification with PEI, the interfacial shear strength and fracture toughness of CF/epoxy composite were increased to 89.9 MPa and 200.3 J m−2, by 64.3% and 149.7%, respectively, in compared with desized CF reinforced epoxy composites.Highlights A rigid‐flexible interface was constructed between CF and epoxy resin. The interfacial strength and toughness of CFRP were synergistically improved. IFSS and interfacial toughness increased by 64.3% and 149.7%, respectively.

P‐265: Tailoring SS of a‐IGZO TFT through Defect Formation Mechanism during PEALD Deposition Sequences

We reported the fabrication of indium‐gallium‐zinc oxide (IGZO) thin‐film transistors (TFTs) by plasma‐enhanced atomic‐layer‐deposition (PEALD) process using different surface reactivities of the precursor‐substrate combinations with controlled deposition sequences. In‐Zn‐Ga (Case II) exhibited favorable subthreshold swing (SS) values of 313 mV/decade, and moderate mobility (µFE) of 29.3 cm2/Vs compared to In‐Ga‐Zn (Case I) (84 mV/decade and 33.4 cm2/Vs).

Integration of conventional surface science techniques with surface-sensitive azimuthal and polarization dependent femtosecond-resolved sum frequency generation spectroscopy.

Experimental insight into the elementary processes underlying charge transfer across interfaces has blossomed with the wide-spread availability of ultra-high vacuum (UHV) setups that allow the preparation and characterization of solid surfaces with well-defined molecular adsorbates over a wide range of temperatures. Within the last 15 years, such insights have extended to charge transfer heterostructures containing solids overlain by one or more atomically thin two dimensional materials. Such systems are of wide potential interest both because they appear to offer a path to separate surface reactivity from bulk chemical properties and because some offer completely novel physics, unrealizable in bulk three dimensional solids. Thick layers of molecular adsorbates or heterostructures of 2D materials generally preclude the use of electrons or atoms as probes. However, with linear photon-in/photon-out techniques, it is often challenging to assign the observed optical response to a particular portion of the interface. We and prior workers have demonstrated that by full characterization of the symmetry of the second order nonlinear optical susceptibility, i.e., the χ(2), in sum frequency generation (SFG) spectroscopy, this problem can be overcome. Here, we describe an UHV system built to allow conventional UHV sample preparation and characterization, femtosecond and polarization resolved SFG spectroscopy, the azimuthal sample rotation necessary to fully describe χ(2) symmetry, and sufficient stability to allow scanning SFG microscopy. We demonstrate these capabilities in proof-of-principle measurements on CO adsorbed on Pt(111) and on the clean Ag(111) surface. Because this setup allows both full characterization of the nonlinear susceptibility and the temperature control and sample preparation/characterization of conventional UHV setups, we expect it to be of great utility in the investigation of both the basic physics and applications of solid, 2D material heterostructures.

Analysis of Altitude and Ambient Temperature Effects on the Reactivity of Oxidation Catalysts in the Presence of H2

Worldwide emission standards are now required to cover engine operation under extreme ambient conditions, which affect the raw emissions and the efficiency of the exhaust aftertreatment systems. These regulations also target new combustion technologies for decarbonization, such as neat hydrogen (H2) combustion or dual-fuel strategies, which involve a challenge to the analysis of exhaust aftertreatment system requirements and performance. This work addresses the impact of high altitude and low ambient temperature conditions on the reactivity of an oxidation catalyst in the presence of H2. A reaction mechanism is proposed to cover the main conversion paths of CO, HC, and H2, including the formation and consumption of high-energy surface reaction intermediates. The mechanism has been implemented into a faster-than-real-time reduced-order model for multi-layer washcoat honeycomb catalytic converters. The model was utilized to investigate the effect of H2 concentration on the reactivity of CO and HC within the catalyst under various operating and ambient conditions. By applying the model and examining the selectivity towards different reaction pathways in the presence of H2, insights into surface intermediates and reactivity across different cross-sections of the monolith were obtained. This analysis discusses the underlying causes of reactivity changes promoted by H2 and its relative importance as a function of driving boundary conditions.

Effects of low-molecular-weight organic acids on the transformation and phosphate retention of iron (hydr)oxides

The retention and mobilization of phosphate in soils are closely associated with the adsorption of iron (hydr)oxides and root exudation of low-molecular-weight organic acids (LMWOAs). This study investigated the role of LMWOAs in phosphate mobilization under incubation and field conditions. LMWOAs-mediated iron (hydr)oxide transformation and phosphate adsorption experiments revealed that the presence of LMWOAs decreased the phosphate adsorption capacity of iron (hydr)oxides by up to ~74 % due to the competition effect, while LMWOAs-induced iron mineral transformation resulted in an approximately six-fold increase in phosphate retention by decreasing the crystallinity and increasing the surface reactivity. Root simulation in rhizobox experiments demonstrated that LMWOAs can alter the contents of different extractable phosphate species and iron components, leading to 10 % ~ 30 % decreases in available phosphate in the near root region of two tested soils. Field experiments showed that crop covering between mango tree rows promoted the exudation of LMWOAs from mango roots. In addition, crop covering increased the contents of total phosphate and available phosphate by 9.08 % ~ 61.20 % and 34.33 % ~ 147.33 % in the rhizosphere soils of mango trees, respectively. These findings bridge the microscale and field scale to understand the delicate LMWOAs-mediated balance between the retention and mobilization of phosphate on iron (hydr)oxide surface, thereby providing important implications for mitigating the low utilization efficiency of phosphate in iron-rich soils.

Caught in the Act of Substitution: Interadsorbate Effects on an Atomically Precise Fe/Co/Se Nanocluster.

Directing groups guide substitution patterns in organic synthetic schemes, but little is known about pathways to control reactivity patterns, such as regioselectivity, in complex inorganic systems such as bioinorganic cofactors or extended surfaces. Interadsorbate effects are known to encode surface reactivity patterns in inorganic materials, modulating the location and binding strength of ligands. However, owing to limited experimental resolution into complex inorganic structures, there is little opportunity to resolve these effects on the atomic scale. Here, we utilize an atomically precise Fe/Co/Se nanocluster platform, [Fe3(L)2Co6Se8L'6]+ ([1(L)2]+; L = CN t Bu, THF; L' = Ph2PN(-)Tol), in which allosteric interadsorbate effects give rise to pronounced site-differentiation. Using a combination of spectroscopic techniques and single-crystal X-ray diffractometry, we discover that coordination of THF at the ligand-free Fe site in [1(CN t Bu)2]+ sets off a domino effect wherein allosteric through-cluster interactions promote the regioselective dissociation of CN t Bu at a neighboring Fe site. Computational analysis reveals that this active site correlation is a result of delocalized Fe···Se···Co···Se covalent interactions that intertwine edge sites on the same cluster face. This study provides an unprecedented atom-scale glimpse into how interfacial metal-support interactions mediate a collective and regiospecific path for substrate exchange across multiple active sites.

Construction of 3D nanostructures on carbon fiber surfaces by sizing for preparing high‐performance composites

AbstractPoor interfacial adhesion between carbon fibers (CF) and the resin matrix has been a limiting factor in advancing the properties of composites. To address this challenge, this study employs the sizing method to coat carbon nanotubes (CNTs) and hexagonal boron nitride nanosheets (h‐BN) onto the CF surface. The 3D structures formed by strategic of combination 1D and 2D nanomaterials, markedly enhances the mechanical, thermal and frictional properties of CF composites. The results reveal a significant boost in the flexural strength, flexural modulus, interlaminar shear strength and interfacial shear strength of the prepared CF composites, registering increases of 53.96%, 60.41%, 55.58% and 55.35%, respectively. These advancements stem from the heightened surface reactivity and roughness of the fibers, facilitated by the synergistic interactions between CNTs and BN. Furthermore, the thermal conductivity of the composites exhibits a remarkable increase of 63.56%, attributed to the synergistic coupling between CF and BN, establishing an efficient thermal conductivity pathway within the composites. This research provides a highly effective approach for crafting high‐performance CF composites.Highlights Construction of 3D network structures on CF surfaces by the sizing method. Synergistic coupling between BN and CNT enhances composite properties. Synergistic enhancement of friction and thermal properties of CF composites.

Structure and Chemical Reactivity of Y-Stabilized ZrO2 Surfaces: Importance for the Water-Gas Shift Reaction.

The surface structure and chemical properties of Y-stabilized zirconia (YSZ) have been subjects of intense debate over the past three decades. However, a thorough understanding of chemical processes occurring at YSZ powders faces significant challenges due to the absence of reliable reference data acquired for well-controlled model systems. Here, we present results from polarization-resolved infrared reflection absorption spectroscopy (IRRAS) obtained for differently oriented, Y-doped ZrO2 single-crystal surfaces after exposure to CO and D2O. The IRRAS data reveal that the polar YSZ(100) surface undergoes reconstruction, characterized by an unusual, red-shifted CO band at 2132 cm-1. Density functional theory calculations allowed to relate this unexpected observation to under-coordinated Zr4+ cations in the vicinity of doping-induced O vacancies. This reconstruction leads to a strongly increased chemical reactivity and water spontaneously dissociates on YSZ(100). The latter, which is an important requirement for catalysing the water-gas-shift (WGS) reaction, is absent for YSZ(111), where only associative adsorption was observed. Together with a novel analysis Scheme these reference data allowed for an operando characterisation of YSZ powders using DRIFTS (diffuse reflectance infrared Fourier transform spectroscopy). These findings facilitate rational design and tuning of YSZ-based powder materials for catalytic applications, in particular CO oxidation and the WGS reaction.

Pyrolysis of shenmu coal to prepare blue-coke used as reductant

Blue-coke is a form of granular char prepared by medium-low temperature pyrolysis of low-rank coal. As a reductant, it has been widely used in calcium carbide production, ferroalloy, copper pyro refining, and ferrosilicon production in China due to the abundant reserves of raw coal and its excellent performance. However, there is little research on the pyrolysis process of granular coal to produce blue-coke and its characteristics as a reductant. Thus, the effects of pyrolysis temperature, heating rate, particle size and holding time at the final temperature on blue-coke preparation were investigated in a rotary kiln reactor. The quality index of blue-coke as a reductant and its properties, including the element composition, surface function groups, carbon forms, reactivity and lower heating value under different pyrolysis temperatures, were analyzed in detail. It is demonstrated that the pyrolysis temperature had a more significant impact on the quality of blue-coke compared to other pyrolysis conditions. With the rise of pyrolysis temperature, the blue-coke’s C/O and C/H increased. With the particle size and heating rate increased, the temperature gradients developed within the granular coal during the pyrolysis process led to the volatile release shifting to higher temperature zone and more secondary reaction occurrence. Nevertheless, the secondary reaction was restrained in the rotary kiln with good heat and mass transfer. The indexes of blue-cokes as reductants were met by the chars produced at temperatures from 550 oC to 750 oC with a holding time 60 min at this temperature and a heating rate of 10 oC/min. As the key index of blue-coke, the electrical resistivity decreased with the increase of pyrolysis temperature. It was found to be closely related to the removal of H and O heteroatom at the pyrolysis temperature below 700 °C. While at the higher temperature, the development of graphitized carbon structure took a major role on it. Nonetheless, the crystallite sizes of the blue-coke obtained under this low temperature pyrolysis were small and the carbon forms were turbostratic. These resulted in the blue-coke's high combustion reactivity, which would gradually decline with the rise of pyrolysis temperature.

Unveiling the Potential Scope of Nanoparticles in the Current Era of Crop Productivity

Nanotechnology, a revolutionary field encompassing the manipulation of matter on an atomic or molecular scale, holds immense potential for upgrading wide areas, including agriculture. Understanding the scope of nanotechnology, researchers have directed their focus towards addressing the challenges in agriculture and enhancing crop productivity. Nanoparticles offer unique properties, including high surface area and reactivity, that can be harnessed to optimize nutrient delivery, mitigate soil toxicity, and enhance plant growth. Various studies have demonstrated the effectiveness of nanoparticles in increasing crop yields, improving nutrient uptake efficiency, and reducing environmental impacts associated with conventional agricultural practices with sustainable agriculture. Nanotechnology overcomes various challenges encountered in traditional agricultural practices including limited availability of nutrients in the soil, inefficient nutrient uptake by plants, soil degradation, and environmental pollution by providing targeted nutrient delivery, improving nutrient absorption, and mitigating environmental impacts. Also, nanoparticle interactions with plants and microbes and strengthening symbiotic relationships by providing active nutrient supplies to microbes. Furthermore, nanoparticles can improve soil structure and fertility by reducing compaction, increasing water retention, and enhancing soil aggregation. These improvements in soil quality not only benefit crop growth but also contribute to sustainable land management practices.This review paper provides an overview of the current research landscape in the application of nanoparticles in agriculture, highlighting key findings, challenges, and future prospects. By leveraging the principles of nanotechnology, agricultural scientists and practitioners aim to revolutionize crop production, meet the needs of farmers, and ensure food security in the face of evolving environmental and socio-economic challenges.

Surfactant-Dependent Partitioning of Organics in Aqueous-Organic Reaction Systems.

A fluorescence lifetime imaging microscopy (FLIM) technique characterizes surfactant-dependent partitioning of organics in a system that mimics a Negishi-like cross-coupling reaction in water, under synthetic concentrations, with emulsion droplets. Experimental partitioning data were not predictable from simple hydrophilic-lipophilic balances. The ionic surfactant cetrimonium chloride suppressed the reactivity of the metallic zinc surface, presumably through competitive chloride binding and concurrent cetrimonium coating, a finding that may contribute to the reduced performance of ionic surfactants in the bench-scale coupling reaction.

Non‐Fluorinated Ethers to Mitigate Electrode Surface Reactivity in High‐Voltage NCM811‐Li Batteries

AbstractLithium (Li) metal batteries (LMBs) with nickel (Ni)‐rich layered oxide cathodes exhibit twice the energy density of conventional Li‐ion batteries. However, their lifespan is limited by severe side reactions caused by high electrode reactivity. Fluorinated solvent‐based electrolytes can address this challenge, but they pose environmental and biological hazards. This work reports on the molecular engineering of fluorine (F)‐free ethers to mitigate electrode surface reactivity in high‐voltage Ni‐rich LMBs. By merely extending the alkyl chains of traditional ethers, we effectively reduce the catalytic reactivity of the cathode towards the electrolyte at high voltages, which suppresses the oxidation decomposition of the electrolyte, microstructural defects and rock‐salt phase formation in the cathode, and gas release issues. The high‐voltage Ni‐rich NCM811‐Li battery delivers capacity retention of 80 % after 250 cycles with a high Coulombic efficiency of 99.85 %, even superior to that in carbonate electrolytes. Additionally, this strategy facilitates passivation of the Li anode by forming a robust solid‐electrolyte interphase, boosting the Li reversibility to 99.11 % with a cycling life of 350 cycles, which outperforms conventional F‐free ether electrolytes. Consequently, the lifespan of practical LMBs has been prolonged by over 100 % and 500 % compared to those in conventional carbonate‐ and ether‐based electrolytes, respectively.