Surface Chemistry Research Articles

SnF2-Catalyzed Lithiophilic-Lithiophobic Gradient Interface for High-Rate PEO-based All-Solid-State Batteries.

Polyethylene oxide (PEO)-based all solid-state lithium metal batteries (ASSLMBs) are strongly hindered by the fast dendrite growth at the Li metal/electrolyte interface, especially under large rates. The above issue stems from the suboptimal interfacial chemistry and poor Li+ transport kinetics during cycling. Herein, a SnF2-catalyzed lithiophilic-lithiophobic gradient solid electrolyte interphase (SCG-SEI) of LixSny/LiF-Li2O is in-situ formed. The superior ionic LiF-Li2O rich upper layer (17.1 nm) possesses high interfacial energy and fast Li+ diffusion channels, wherein lithiophilic LixSny alloy layer (8.4 nm) could highly reduce the nucleation overpotential with lower diffusion barrier and promote rapid electron transportation for reversible Li+ plating/stripping. Simultaneously, the insoluble SnF2-coordinated PEO promotes the rapid Li+ ion transport in the bulk phase. As a result, an over 46.7 and 3.5 times improvements for lifespan and critical current density of symmetrical cells are achieved, respectively. Furthermore, LiFePO4-based ASSLMBs deliver a recorded cycling performance at 5 C (over 1000 cycles with a capacity retention of 80.0%). More importantly, impressive electrochemical performances and safety tests with LiNi0.8Mn0.1Co0.1O2 and pouch cell with LiFePO4, even under extreme conditions (i.e., 100 ℃), are also demonstrated, reconfirmed the importance of lithiophilic-lithiophobic gradient interfacial chemistry in the design of high-rate ASSLMBs for safety applications.

Pitfalls and Challenges of Peptide Nucleic Acid Immobilisation on Carbon Surfaces for Sequence-specific Capturing of Nucleic Acid Biomarkers

Nucleic acid sensors based on a peptide nucleic Acid (PNA) probe have seen a surge in interest since their discovery in the 1990s, and after the patent protecting them expired in 2013. The appeal of PNA as capture and/or sensing probes as an alternative to standard DNA or RNA oligonucleotides originates from their superior chemical stability and affinity for complementary oligonucleotides, as well as their increased responsiveness to single base mismatches. The implementation of PNA probes onto optical and electrochemical sensors has showed great promise although progress has been hampered by issues mostly associated with surface chemistry, probe accessibility and non-specific binding. Herein, we report on a systematic comparison between various PNA immobilisation strategies on carbon substrates based on both covalent and non-covalent chemistries. Besides the use of standard electrochemical techniques to characterise the extent of surface modification, the ability of immobilised PNAs to engage in chemical interactions with freely diffusing molecule was also investigated. Using original chemical tags, this study provides a unique insight into the impact of immobilisation chemistries on PNA’s (bio)availability. Rapid immobilisation of biotinylated PNA oligomers on screen-printed carbon electrode (SPCE) coated with adsorbed polystreptavidin (pSA) demonstrated highest efficiency and ease in the preparation process. An original nucleic acid sensor using this immobilisation chemistry is reported that is based on a sandwich assay between a surface bound PNA capture probe and a freely diffusing electrochemically active PNA sensing probe.

Controlling the structure of nitrogen-doped zeolite-templated carbon for CO2 capture based on the synthesis conditions

The surface chemistry and the textural properties of nitrogen-doped zeolite-templated carbon materials (N-ZTC) are decisive for their functionality in CO2 capture. This study analyses how the synthesis conditions affect the structure, formation of N-containing functional groups, thermal stability and CO2 capture of N-ZTC in comparison with nitrogen-free ZTC. Faujasite as a hard template and chemical vapour depositions (CVD) with propene and acetonitrile were used for the synthesis of ZTC and N-ZTC, respectively. XRD, SEM, N2 and CO2 sorption, XPS and TG/DSC analyses showed that the structural ordering and microporous volume in N-ZTC increases with increasing synthesis temperature. Conversely, at higher temperatures, the content of basic pyridinic groups in N-ZTC decreases in favour of stable graphitic nitrogen. The Lewis acid−base interaction of CO2 with the pyridinic groups provides the highest adsorption heats, the highest affinity for CO2 compared to N2 and enhances CO2/N2 selectivity (CO2/N2 selectivities of 127, 95, 89, and 66 for N-ZTC750°C, N-ZTC800°C, N-ZTC850°C and ZTC, respectively). The maximum adsorption capacity was achieved for N-ZTC800°C still yielding a high content of basic groups and a larger micropore volume compared to N-ZTC750°C. The decisive factor for the selectivity is thus the presence of basic centres attainable in N-ZTC at a lower synthesis temperature. The maximum adsorption capacity is associated with a large microporous volume and basic centres in N-ZTC synthesised at medium temperatures. The energy of CO2 adsorption by Lewis acid−base interactions and well-developed micropores are decisive for high selectivity and large adsorption capacity for efficient CO2 capture using N-ZTC materials.

Investigation of mechanical and physico-chemical properties of new natural fiber extracted from Bassia indica plant for reinforcement of lightweight bio-composites

In this investigation, novel cellulose fibers were acquired from the Bassia Indica plant to serve as a reinforcement source in composite materials. The morphological characteristics were studied using Scanning Electron Microscopy (SEM). The surface chemistry, crystallinity, and functional groups of Bassia Indica fibers were analyzed using X-ray Diffraction (XRD), Energy Dispersive X-ray (EDX) spectroscopy, and Attenuated Total Reflectance-Fourier Transform Infrared spectroscopy (ATR-FTIR), which assess the crystal structure, elemental composition, and surface functional groups, respectively. The thermal behavior of Bassia Indica fibers were assessed through Thermogravimetric Analysis (TGA). Anatomical techniques demonstrated the abundant presence of fibroblasts in the fibers. The presence of lignocellulosic fiber (lignin, cellulose and hemicellulose) was confirmed through ATR-FTIR analysis. The analysis of physical properties unveiled a fiber density of 1.065 ± 0.025 g/cm³ and a diameter of 145.58 ± 7.89 μm. The crystalline size of Bassia Indica fibers reached 2.23 nm, with a crystallinity index of 40.12 %, and an activation energy of 93.78 kJ/mol, TGA research revealed that Bassia Indica fibers are thermally stable up to 260.24 °C. Additionally, the fibers experienced maximum degradation at 321.23 °C. Weibull statistical analysis was performed using parameters 2 and 3 to calculate the observed dispersion in the experimental tensile results after analyzing the mechanical properties of the fibers possessing a tensile strength of 417.50 ± 7.08 MPa, Young's modulus of 17.46 ± 1.55 GPa, stress at failure of 1.17 ± 0.02 % and interfacial shear strength of 6.99 ± 1.10 MPa. The results were additionally compared to how they were stated in the relevant sources. Bassia Indica fibers can be considered a viable choice for reinforcing lightweight bio-composites.

Comparative assessment of biochar produced from waste biomass in laboratory furnace and industrial screw reactor systems

Biochar is rapidly gaining traction as a commercially viable carbon dioxide removal (CDR) technology that can be applied globally at various scales. However, the vast majority of published research studies have involved laboratory experiments conducted in an inert environment under well-controlled conditions of heating rate, maximum temperature and residence time. To expand the biochar industry within the next decade as a CDR platform, there is a need to understand differences between biochar produced under “ideal” laboratory conditions versus those generated using the same feedstocks in continuous, industrial scale systems. In the present work, biochar was produced from widely available organic waste feedstocks, including mixed cafeteria food waste, blended coffee grounds and chaff, grape pomace and wood pellets, using both a laboratory furnace operated in a nitrogen environment, and a continuously operated commercial system capable of processing up to ~1 t/day of dry feedstock. High quality biochar (H:C < 0.7) was obtained for all feedstocks converted by both systems, however high variability in volatiles and decomposition rates was observed in the thermogravimetric analysis (TGA) results for industrial scale biochar. Scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR) showed similar morphologies and surface chemistries in both laboratory and industrial scale samples, in agreement with reported literature data. Based on this initial comparative assessment, we conclude that commercially available thermochemical systems have potential as localized organic waste valorization technologies to produce high quality biochar. We identified important control variables that have the greatest effect on the resulting biochar. Despite the reported differences between biochar materials derived from the same feedstock, key properties critical for soil amendment and remediation applications (i.e., H:C, surface area, %Corg, etc.) are reasonably consistent between laboratory and continuously fed equipment typical of commercial-scale systems. Thus, biochar materials obtained from well-controlled laboratory experiments conducted in a pure nitrogen atmosphere can be reasonably representative of biochar produced from the same feedstocks using industrial scale equipment.

Hierarchically porous carbon foams coated with carbon nitride: Insights into adsorbents for pre-combustion and post-combustion CO2 separation

Adsorption is fundamental to many industrial processes, including separation of carbon dioxide from other gases in pre- or post-combustion gas mixtures. Adsorbents should have high capacity and selectivity, which are both intimately linked with surface area, pore size distribution, and surface energy. Porous carbons are cheap and scalable adsorbents, but greater understanding of how their textural properties and surface chemistry affects their performance is needed. Here, we investigate the effect of nitrogen doping on CO2 adsorption. Microporous carbon foams with large surface area (>2500 m2 g−1) and pore volume (1.6 cm3 g−1) are synthesized, then coated with varying amounts of carbon nitride (up to 17 at% nitrogen) to achieve high CO2 uptake (25.5 mmol g−1) and selectivity (CO2:N2 = 21), whilst also giving insights into the relationship between structure and function. At low pressure (relevant to post-combustion capture), moderate carbon nitride loading leads to enhanced uptake and selectivity by combining large ultramicropore volume with the introduction of Lewis base sites, leading to high isosteric heat of adsorption. Higher carbon nitride loading further increases selectivity but lowers uptake by blocking micropores. Conversely, at high pressure (relevant to pre-combustion capture) the uncoated carbon foam displays superior uptake, because mesoporosity is the dominant factor in this regime, rather than the presence of ultramicropores. Finally, the samples displayed excellent regeneration under repeated adsorption–desorption cycles, and breakthrough curves were measured. These results underscore the delicate balance required for optimal material design when applying porous carbon adsorbents to CO2 separation processes. Moving forward, improved adsorbents will contribute to the proliferation of carbon capture and storage (CCS) and carbon capture and utilisation (CCU) technologies, ultimately contributing reduced anthropogenic CO2 emissions.

Design and engineering of 3D plasmonic superstructure based on Pickering emulsion templates for Surface-Enhanced Raman spectroscopy applications in chemical and biomedical sensing

The integration of Pickering emulsion as a versatile template facilitates the assembly of nanoscale and microscale NPs, leading to the formation of intricate 3D superstructures. These superstructures exhibit collective properties, including optical, electric, and catalytic functionalities, surpassing individual building block. This review comprehensively explores the design and engineering principles behind the creation of these multifaceted superstructures. The exploration begins with the fundamental aspects of surface chemistry governing nanoparticles, a crucial factor in directing their assembly behavior at the curved liquid–liquid emulsion interface. Emphasis is placed on understanding emulsion stability, a pivotal element guiding the formation of stable 3D architectures. The discussion extends to unraveling the underlying mechanisms promoting the formation of these 3D superstructures. The focus lies in elucidating the optical functionalities of these superstructures, particularly in the context of surface-enhanced Raman spectroscopy application. The surveyed literature showcases diverse Pickering emulsion-based strategies employed in the assembly of plasmonic nanoparticles into intricate superstructures, offering controlled architectures and unlocking unique potentials for chemical and biochemical sensing.

Effect of physicochemical properties on critical sinking and attachment of respirable coal mine dust impacting on a water surface

Respirable coal mine dust (RCMD) inhalation is identified as the main cause of the resurgence of coal worker’s pneumoconiosis (CWP) since the mid-1990s. At present, the predominant dust control technology is the water spray system. However, in practice, the capture efficiency of RCMD by this technology is relatively low. To understand the capturing mechanism and develop improvement strategies, this research is focused on the surface chemistry study of RCMD and its impact on a water surface using a dynamic model. Proximate analysis, chemical, and mineral composition of a run-of-mine (ROM) coal sample from Appalachian region were analyzed using a proximate analyzer, Inductively Coupled Plasma Mass Spectrometry (ICP-MS), and X-ray Diffraction (XRD), respectively. Contact angles were measured by capillary rise test using the Washburn equation. Based on the dynamic model, the effects of particle size, density, contact angle, and surface tension on the critical sinking were investigated. It was pointed out in this work that reducing surface tension, in turn, decreases contact angle, which has been neglected in the literature. Regime maps for different minerals were created and showed that organic matter has the highest critical velocity due to its low density and high contact angle. Reducing water surface tension to the critical solid surface tension of coal around 30 mN/m could maximize the attachment efficiency. Scaling laws, constructed by force balance, led to the criteria of critical sinking: Ucr61-cosθ2D+1γlvρlR, i.e., Wecr121-cosθ2D+1. A semi-empirical formula for critical velocity was obtained by fitting the simulation data, Ucr=1.0961-cosθ2D+1γlvρlR. Attachment efficiency was defined and formulated as Pa=U02Ucr2=We0Wecr, establishing relationships between attachment efficiency and the physicochemical properties of RCMD and water droplets

Advancing Metallic Lithium Anodes: A Review of Interface Design, Electrolyte Innovation, and Performance Enhancement Strategies

Lithium (Li) metal is one of the most promising anode materials for next-generation, high-energy, Li-based batteries due to its exceptionally high specific capacity and low reduction potential. Nonetheless, intrinsic challenges such as detrimental interfacial reactions, significant volume expansion, and dendritic growth present considerable obstacles to its practical application. This review comprehensively summarizes various recent strategies for the modification and protection of metallic lithium anodes, offering insight into the latest advancements in electrode enhancement, electrolyte innovation, and interfacial design, as well as theoretical simulations related to the above. One notable trend is the optimization of electrolytes to suppress dendrite formation and enhance the stability of the electrode–electrolyte interface. This has been achieved through the development of new electrolytes with higher ionic conductivity and better compatibility with Li metal. Furthermore, significant progress has been made in the design and synthesis of novel Li metal composite anodes. These composite anodes, incorporating various additives such as polymers, ceramic particles, and carbon nanotubes, exhibit improved cycling stability and safety compared to pure Li metal. Research has used simulation computing, machine learning, and other methods to achieve electrochemical mechanics modeling and multi-field simulation in order to analyze and predict non-uniform lithium deposition processes and control factors. In-depth investigations into the electrochemical reactions, interfacial chemistry, and physical properties of these electrodes have provided valuable insights into their design and optimization. It systematically encapsulates the state-of-the-art developments in anode protection and delineates prospective trajectories for the technology’s industrial evolution. This review aims to provide a detailed overview of the latest strategies for enhancing metallic lithium anodes in lithium-ion batteries, addressing the primary challenges and suggesting future directions for industrial advancement.

Surface engineering of carbon nanotube-carbon fiber networks for enhanced strength in additive manufacturing of nylon composites

This work quantifies the impact of chemical functionalization of carbon nanotubes and carbon fibres on the interfacial shear strength, tensile and interlaminar shear strength properties of additively manufactured nylon composites. The surface chemistry of functionalized carbon materials was evaluated through infrared spectroscopy, energy-dispersive X-ray spectroscopy, and X-ray photoelectron spectroscopy. Single carbon fibre was dip-coated in a suspension of nanotubes and embedded into a nylon matrix. The fibres were pulled out to measure the interfacial shear strength, and the fibres with attached neat, carboxylated, and silanized nanotubes increased it by up to 67 %, 112 %, and 216 %, respectively. Composite samples were manufactured using a novel hybrid additive manufacturing method, which was able to deposit nylon layers and a suspension containing carbon reinforcement. The use of chemically functionalized nanotubes in the suspension led to carbon layers that improved tensile strength by 49 % and tensile modulus by 126 % over neat nylon. Functionalization of carbon reinforcement increased the interlaminar shear strength by up to 63 %. Overall, this paper demonstrates the importance of chemical modification in composite materials containing a large interface area of carbon materials.

Impact of Binder Thin-Films on Surface Chemistry of Silicon Anodes in Lithium-Ion Batteries

Abstract The effect of polymer binder on the nature and location of solid-electrolyte interphase (SEI) formation on Si active material was investigated. Thin layers of polymeric binder (polyvinylidene fluoride and sodium carboxymethyl cellulose) were spin-coated onto polished single crystal Si wafers. The samples were cycled against a Li counter/reference electrode under various electrochemical conditions in a coin cell configuration. The electrolyte was 1 M of LiPF6 in 1:1:1 wt % EC:DEC:DMC. After cycling, the samples were extracted from the coin cell under inert conditions and X-ray photoelectron spectroscopy (XPS) was performed. Electron microscopy and atomic force microscopy indicate that the binder films are smooth and continuous across the wafer surface, and no impact on the electrochemical behavior was observed. However, notable differences were detected using XPS, which revealed both difference in SEI composition and location relative to the binder-electrolyte and binder-substrate interfaces. These observations and insights will be useful in cell designs, binder selection, and reliability estimates because the location of SEI formation may influence cyclic performance of electrodes.

Co-regulating the pore structure and surface chemistry of sludge-based biochar for high–performance deodorization of gaseous dimethyl disulfide

A straightforward and eco-friendly preparation method for porous sludge biochar (SBA-3) was developed to deodorize gaseous dimethyl disulfide (DMDS) using ion exchange to adjust micropore structures coupled with carboxyl functionalization. Compared with the unmodified sludge biochar SBA-1 and SBA-2 treated with ion exchange, the pore size of SBA-3 decreased accompanied with increasing specific surface area and micropore volume. The Brunauer–Emmett–Teller (BET) specific surface area and micropore volume were 176.35 m2 g−1 and 0.0314 cm³ g−1, which were 2.02 and 1.71-fold larger than those of SBA-2, as well as 20.60 and 78.5-fold larger than those of SBA-1, respectively. Meanwhile, the amount of –COOH on the surface of SBA-3 increased from 0.425 to 1.123 mmol g−1, which was 2.64-fold larger than that of SBA-1. The adsorption behavior between DMDS and SBA-3 could be well described by the quasi-second-order kinetic model and Langmuir isotherm model. The maximum monolayer adsorption capacity was 35.12 mg g−1 at 303 K. Thermodynamic and DFT calculations indicated that the adsorption of DMDS on SBA-3 was exothermic with the deodorization mechanisms involving pore filling and chemisorption.

Osteointegration of Ti Bone Implants: A Study on How Surface Parameters Control the Foreign Body Response.

The integration of titanium (Ti)-based implants with bone is limited, resulting in implant failure. This lack of osteointegration is due to the foreign body response (FBR) that occurs after the implantation of biodevices. The process begins with protein adsorption, which is governed by implant surface properties, e.g., chemistry, charge, wettability, and/or topography. The distribution and composition of the protein layer in turn influence the recruitment, differentiation, and modulation of immune and bone cells. The subsequent events that occur at the bone-material interface will ultimately determine whether the implant is encapsulated or will integrate with bone. Despite the numerous studies evaluating the influence of surface properties in the various stages of the FBR, the factors that affect tissue-material interactions are often studied in isolation or in small correlations due to the technical challenges involved in assessing them in vitro or in vivo. Consequently, the influence of protein conformation on the Ti bone implant surface design remains an unresolved research question. The objective of this review is to comprehensively evaluate the existing literature on the effect of surface parameters of Ti and its alloys in the stages of FBR, with a particular focus on protein adsorption and osteoimmunomodulation. This evaluation aims to systematically describe these effects on bone formation.

G-C3N4-based photocatalytic materials for converting CO2 into energy: a review.

Environmental pollution management and renewable energy development are humanity's biggest issues in the 21st century. The rise in atmospheric CO2, which has surpassed 400 parts per million, has stimulated research on CO2reduction and conversion methods. Presently, photocatalytic conversion of CO2to valuable hydrocarbons enables the transformation of solar energy into chemical energy and offers a novel avenue for energy conversion while regulating the greenhouse effect. This is an ideal strategy for simultaneously addressing environmental issues and the energy crisis. Photocatalysts are essential to photocatalytic processes. Photocatalyst is the core of photocatalytic technology, and graphite carbon nitride (g-C3N4) has attracted much attention because of its nonmetallic characteristics, and it has the characteristics of low cost, tunable electronic structure, easy manufacture and strong reducibility. However, its activity is not only affected by external reaction conditions, but also by the band gap structure, physical and chemical stability, surface morphology and specific surface area of the photocatalyst it. In this paper, the application progress of g-C3N4-based photocatalytic materials in CO2reduction is reviewed, and the modification strategies of g-C3N4-based catalysts to obtain better catalytic efficiency and selectivity in CO2photocatalytic reduction are summarized, and the future development of this material is prospected.

Comparison and mechanism analysis of MgO, CaO, and Portland cement for immobilization of heavy metals in MSWI fly ash

The significant production of municipal solid waste incineration fly ash (MSWI FA) underscores the importance of developing efficient solidification materials. This study employed MgO and CaO for immobilizing MSWI FA (with a 70% fly ash incorporation), and the immobilization effect was compared with that of Portland cement (PC). Experimental findings revealed that MgO exhibited the most effective stabilization for heavy metals (Cd, Cu, Pb, and Zn) compared to CaO and PC. XRD, FTIR, TG, and SEM analysis indicated that the principal hydration products in MSWI FA binders solidified with MgO, CaO, and PC were Mg(OH)2, CaCO3, and C-S-H gel, respectively. Mg(OH)2 efficiently immobilized heavy metals through chemical complexation and surface adsorption mechanisms. The MgO-treated MSWI FA demonstrated the highest residual fractions and the lowest easily leachable fractions. Moreover, the leaching characteristics of heavy metals were significantly influenced by the pH level, so MgO-treated MSWI FA with a leachate pH of 9.18 achieved the precipitation and stabilization of most heavy metals. In summary, this study provided an effective material selection for MSWI FA immobilization and presented a novel strategy for MSWI FA management.

Spiky Gold Nanoparticles, a Nanoscale Approach to Enhanced Ex Vivo T-Cell Activation.

While existing synthetic technologies for ex vivo T-cell activation face challenges like suboptimal expansion rates and low effectiveness, artificial antigen-presenting cells (aAPCs) hold great promise for enhanced T-cell based therapies. In particular, gold nanoparticles (AuNPs), known for their biocompatibility, ease of synthesis, and versatile surface chemistry, are strong candidates for use as nanoscale aAPCs. In this study, we developed spiky AuNPs with branched geometries to present activating ligands to primary human T-cells. The special structure of spiky AuNPs enhances biomolecule loading capacity and significantly improves T-cell activation through multivalent binding of costimulatory ligands and receptors. Our spiky AuNPs outperform existing systems including Dynabeads and soluble activators by promoting greater polyclonal expansion of T-cells, boosting sustained cytokine production, and generating highly functional T-cells with reduced exhaustion. In addition, spiky AuNPs effectively activate and expand CD19 CAR-T cells while demonstrating increased in vitro cytotoxicity against target cells using fewer effector cells than Dynabeads. This study underscores the potential of spiky AuNPs as a powerful tool, bringing new opportunities to adoptive cell therapy applications.

Nanofibrous La0.95K0.05MnO3 perovskite with improved photoelectrical properties for photocatalytic degradation of antibiotics

Potassium doped lanthanum manganese perovskite oxides, La1−xKxMnO3, with nanofibrous structure, are prepared and used for Photo-Fenton degradation of antibiotics, including ciprofloxacin (CIP), tetracycline (TC), and sulfathiazole (ST). Effects of K doping on the textural structure, optical property, band gap and surface chemistry of LaMnO3 are investigated, showing that La0.95K0.05MnO3 (LKMO-5) has the optimal properties. The photoelectric measurements, including photoluminescence (PL), photocurrent response (PCR) and electrochemical impedance spectroscopy (EIS), also suggest that the LKMO-5 has the best electron–hole separation efficiency, the most amounts of irradiated electrons and the lowest impedance. Photocatalytic tests indicate that LKMO-5 not only shows the best activity for CIP degradation, but also exhibits good stability in the reaction, with negligible activity loss within four cycles. Mechanism investigations, explored by the radical trapping experiments and with the reference of band positions, indicate that superoxide radical ions (·O2−) and holes (h+) are the major reactive species of the reaction.

Surface oxygen vacancy regulation and active metal doping for Cu-Al based spinel catalysts synthesis toward high-efficiency reverse water-gas shift reaction

The reverse water-gas shift (RWGS) reaction is of great significance to convert CO2 to valuable feedstocks. Reasonable design and preparation of catalysts is necessary to achieve high CO2 conversion and CO selectivity. In this study, a series of Cu-Al based spinel catalysts were synthesized by coprecipitation-calcination method or A-site doped with active metal (Co, Zn, Mg, and Fe) for the RWGS reaction. The results indicated that the surface oxygen vacancies and crystal structure of CuAl2O4 can be regulated by calcination temperature. Remarkably, the CuAl-800 catalyst exhibits the highest CO2 conversion rate (62.7 %) with 100 % CO selectivity at 500 °C. Excessive calcination temperatures (> 800 °C) resulted in a well-defined spinel structure, but decreased surface oxygen vacancies and CO2 conversion rate. At calcination temperatures < 800 °C, surface oxygen vacancies increased, but the formation of CuO impurities which irreversibly converted to Cu2O during reduction, decreased catalytic activity. Compared with Zn, Mg and Fe, Co doping can significantly improved the reactivity of CuAl2O4 catalyst in RWGS reaction at 500 °C, increasing the CO2 conversion rate by 8 % while maintaining 100 % CO selectivity. The main reason is that Co doping not only effectively improves the integrity and stability of spinel structure of CuAl2O4, but also enhances its ability to dissociate and activate H species through interfacial sites of CuO-OV-CuXCo1-XAl2O4, thus further enhancing its catalytic conversion ability of CO2 to CO. These results enrich the understanding of surface chemistry of CuAl2O4 spinel and lay an important theory foundation for design of spinel-based catalysts for RWGS reaction.

NO2 Adsorption on Biochar Derived from Wood Shaving Litter: Understanding Surface Chemistry and Adsorption Mechanisms

NO2 Adsorption on Biochar Derived from Wood Shaving Litter: Understanding Surface Chemistry and Adsorption Mechanisms

N2 as an Efficient IR Probe Molecule for the Investigation of Ceria-Containing Materials

Ceria and ceria-based catalysts are very important in redox and acid-base catalysis. Nanoceria have also been found to be important in biomedical applications. To design efficient materials, it is necessary to thoroughly understand the surface chemistry of ceria, and one of the techniques that provides such information about the surface is the vibrational spectroscopy of probe molecules. Although the most commonly used probe is CO, it has some disadvantages when applied to ceria and ceria-based catalysts. CO can easily reduce the material, forming carbonate-like species, and can be disproportionate, thus modifying the surface. Here, we offer a pioneering study of the adsorption of 15N2 at 100 K, demonstrating that dinitrogen can be more advantageous than CO when studying ceria-based materials. As an inert gas, N2 is not able to oxidize or reduce cerium cations and does not form any surface anionic species able to modify the surface. It is infrared and transparent, and thus there is no need to subtract the gas phase spectrum, something that often increases the noise level. Being a weaker base than CO, N2 has a negligible induction effect. By using stoichiometric nano-shaped ceria samples, we concluded that 15N2 can distinguish between surface Ce4+ sites on different, low index planes; with cations on the {110} facets and on some of the edges, Ce4+−15N2 species with IR bands at 2258–2257 cm−1 are formed. Bridging species, where one of the N atoms from the molecule interacts with two Ce4+ cations, are formed on the {100} facets (2253–2252 cm−1), while the interaction with the {111} facets is very weak and does not lead to the formation of measurable amounts of complexes. All species are formed by electrostatic interaction and disappear during evacuation at 100 K. In addition, N2 provides more accurate information than CO on the acidity of the different OH groups because it does not change the binding mode of the hydroxyls.