Layered Precursors Research Articles

Nitrogen functionalized biomass derived mesoporous carbon nanomaterials for electrochemical detection of lead (II) ions

This study has explored the sustainable solution after designing an economical metal-free biomass-derived nanocarbon for the selective sensing of lead. The nitrogen and sulfur-rich mesoporous nanocarbon is designed through a facile hydrothermal-assisted thermal annealing method. The high-temperature treatment gave nanocarbon unique carbon dot decorated layered morphology, while nitrogen and sulfur precursor thiourea and melamine strengthened the nanomaterial stability, sensitivity, and selectivity toward lead metal ions. The high specific surface area of mesoporous nanocarbon viz., 1671.93 m2/g with the pore width and pore volume of 2.02 nm and 0.476 cm3/g has enhanced the conductivity of as-synthesized sensor, which helps in increasing sensitivity toward lead. The high conductivity was also confirmed through cyclic voltammetry, where an 80 % increment in current was observed in the case of the modified electrode when compared with bare GCE. The differential pulse normal voltammetry and differential pulse anodic stripping voltammetry were performed to calculate the detection limit, where an excellent detection limit of 22 nM was obtained from the DPASV technique. Moreover, the nanomaterial was also tested for detecting lead in tap water. The as-synthesized nanocomposite is highly efficient and selective for the detection of lead. This study will motivate the researchers to engineer sustainable and efficient devices for sensing metal pollutants.

Capturing Different Intermediate Phases during Zeolite Synthesis.

Despite extensive efforts over the past several decades, the current mechanistic understanding of zeolite crystallization is still far from satisfactory, thus precluding the synthesis of designer zeolites. Here we show that the nucleation and in situ transformation pathways during the synthesis of medium-pore zeolite TNU-9 can be altered by controlling the extent of cooperative structure direction between Na+ and Cs+ ions in the presence of 1,4-bis(N-methylpyrrolidinium)butane cations as an organic structure-directing agent. The intermediate phase selectivity was found to change from bikitaite to analcime to layered MCM-22 precursor when the gel Na/Cs ratio was adjusted to 7, 15, and 20, respectively. We also show that the transformation of bikitaite into TNU-9 begins at the surface of intermediate crystals, unlike that of analcime and MCM-22 precursor by a dissolution-recrystallization process. The force field simulation results suggest that the nucleation of different intermediate phases is not thermodynamically but kinetically controlled. This study provides a new basis for advancing the fundamental understanding of zeolite crystallization pathways.

Performance activation mechanism of aluminum-based layered double hydroxides adsorbents for recovering Li+ by pH modulating

Aluminum-based adsorbents, simply prepared by eluting the lithium-aluminum layered double hydroxide precursors with deionized water, is the only industrialized adsorbents for selectively separating Li+ from saline brines. Taking the roles of lattice and surface Li+ active sites on its performances into consideration, influence of ending pH modulating on prominently improving the adsorbing capacity and stability of aluminum-based adsorbents prepared by precipitation method is initially investigated. As experimentally evidenced that, the maximum desorption amount of Li+ at the eluting stage should be controlled to around 20 mg/g Li+ rather than thoroughly removed to effectively avoid the topotactic solid-phase transformation from adsorbent to α-Al(OH)3. As-prepared adsorbents not only has high adsorption capacity up to 8.4 mg/g in 400 ppm LiCl solution, but also owns unique self-healing ability, thus promising the excellent cycling stability. It is firstly proposed that the formation of the layer-structured precursor by precipitation method is well in accordance with the three-step formation mechanism and pH modulating mainly contributes to the anions exchange between solution Cl- and interlayer OH–. This study experimentally proves the importance of pH adjusting for preparing high performance lithium adsorbents by precipitation method, which is very significant and important for effectively extracting lithium resources from the complicated multi-component liquid minerals.

Effect of defect-healing treatment on layered silicate precursors toward well-defined crosslinked frameworks.

The synthesis of zeolites from two-dimensional layered precursors through interlayer crosslinking of the layers is a promising avenue for realizing meticulously designed synthesis routes. However, the presence of defective silanol species in the precursors hinders the achievement of desirable synthesis outcomes. This study focuses on PREFER-a layered precursor for FER-type zeolites-which was synthesized and subjected to a liquid-mediated defect-healing treatment that we recently developed. The defect-healing process involves the use of fluoride compounds for reconstruction and organic pore fillers to stabilize the framework. The effects of the treatment on the structure, composition, and iron insertion behavior of PREFER were examined. Characterization results revealed a reduction in the number of intralayer silanol defects, whereas interlayer silanols were unaffected by the defect-healing treatment. Furthermore, the subsequent alterations observed in the crosslinking behavior with iron atoms indicated that the defect-healing treatment may enhance the insertion of iron species between the layers in more homogeneous environments compared with the untreated precursor. These findings provide valuable insights into the prospects of controlled interlayer linkage in two-dimensional zeolite materials.

Ultra-stable Co3O4/NiCo2O4 double-shelled hollow nanocages as headspace solid-phase microextraction coating for enhanced capture of polychlorinated biphenyls

Polychlorinated biphenyls (PCBs) are persistent toxic pollutants that tend to accumulate in food and cause damage to human health. This work reports the ultra-sensitive detection of PCBs in beverage samples (green tea, honey, and bottled drinking water) by headspace solid-phase microextraction (HS-SPME) coupled with a gas chromatography-flame ionization detector (GC-FID). The Ultra-stable Co3O4/NiCo2O4 double-shelled hollow nanocages (DSHNC) as SPME fiber coating were synthesized with pyrolysis of zeolitic imidazolate framework-67/layered double hydroxide precursor. The fiber coating material Co3O4/NiCo2O4 DSHNC demonstrated excellent thermal stability (＞1000 °C) and long usage lifespan (≥160 times). The extract ability to polar PCBs was significantly enhanced by oxygen-containing groups, π-π stacking, and electrostatic interaction. Experiments results illustrated that the adsorption is controlled by chemical adsorption with a monolayer molecular adsorption. The HS-SPME-GC-FID method possessed good linearity (R2 ≥ 0.9961) in the linear range of 0.10–50000 pg·mL−1 and low detection limits (0.03–1.5 pg·mL−1). The enrichment factors were determined between 6884 and 9765. The method was successfully applied to enrich PCBs in real samples and obtained a good recovery rate in the range of 78.26–112.1 %.

A green and environmentally benign route to synthesizing Z-scheme Bi2S3-TCN photocatalyst for efficient hydrogen production.

Designing and developing photocatalysts with excellent performance in order to achieve efficient hydrogen production is an important strategy for addressing future energy and environmental challenges. Traditional single-phase photocatalytic materials either have a large bandgap and low visible light response or experience rapid recombination of the photogenerated carriers with low quantum efficiency, seriously hindering their photocatalytic applications. To solve these issues, an important solution is to construct well-matched heterojunctions with highly efficient charge separation capabilities. To this end, an in situ sulfurization reaction was adopted after the deposition of Bi3+ supramolecular complex on a layered supramolecular precursor of tubular carbon nitride (TCN). X-ray diffraction (XRD) patterns confirmed that the as-prepared sample has a good crystalline structure without any other impurities, while high-resolution transmission electron microscopy (HR-TEM) revealed that the heterojunction possesses a 2D structure with a layer of nano-array on its surface. Combined Fourier-transform infrared (FT-IR) spectra and energy-dispersive X-ray spectroscopy (EDX) revealed the interfacial interactions. Owing to the formation of the Z-scheme heterojunction, the visible light adsorption and the separation efficiency of the photo-generated carriers are both obviously enhanced, leaving the high energy electrons and high oxidative holes to participate in the photocatalytic reactions. As a result, the photocatalytic hydrogen evolution rate of Bi2S3-TCN achieves 65.2μmolg-1·h-1. This proposed green and environmentally benign route can also be applied to construct other sulfides with 2D TCN, providing some important information for the design and optimization of novel carbon-nitride-based semiconductors.

Layered oxide precursor strategy for the synthesizing of titanium oxynitrides

Oxynitride is a mixture of mixed oxide and nitride anions. The creation of simple synthesis methods remains a challenge. Herein, we propose a synthetic method that uses the layered oxide Cs0.68Ti1.83O4 precursor to directly create oxynitride Ti2.85O4N without the need for ammonia. Using a topochemical reaction at 500 °C, a combination of solid Cs2CO3 and TiO2 was converted into the layered oxynitride Cs0.68+xTi1.83O4-xNx.‬‬‬‬‬‬ The crystal structure of Ti2.85O4N has been analyzed by Rietveld refinement with synchrotron radiation data. The UV–Vis spectra revealed that Ti2.85O4N has an absorption edge around 650 nm. Ti2.85O4N exhibits photocatalytic activity for hydrogen evolution utilizing methanol as a reversible electron donor in the visible range (λ > 420 nm) when promoted by platinum. In contrast, the intermediate oxynitride Cs0.68+xTi1.83O4−xNx with surface NHx species does not exhibit photocatalytic activity. These findings open new opportunities for novel titanium oxynitrides photocatalysts.‬‬‬‬‬‬‬

Investigation of the electrochemical performance and structural stability of O6-type lithium-rich layered oxide as a positive electrode active material for improved lithium battery performance

A cobalt-free manganese-based lithium-rich layered oxide with an unusual O6-type structure has been successfully synthesized by solid-state ion-exchange reaction from a P2-type sodium-based layered oxide precursor using LiCl at moderate temperature.

Efficient electrocatalytic reduction of nitrate to ammonia over Mo2CTx micro-foam with rich edge sites

By employing a new method, we directly synthesized the first Mo2C nanosheet based micro-foam with rich edge-sites from the layered m-Mo2CTx precursor. Using this composite towards the electrocatalytic nitrate reduction to ammonia (NRA) at an optimized potential we measured an ammonia yield of 130.8 mmol h−1 g−1cat and a Faradaic Efficiency (FE) of 94.4%, much higher than that measured over the stacked layered structure (17.3 mmol h−1 g−1cat, 44%). This is due to both the large specific surface area of micro-foam and its rich Mo edge-sites, where the Mo and C atom layers are alternatively stacked. Compared with the pure Mo atoms on the basal plane of Mo2C, the Mo edge-sites show a more appropriate bonding with the N atoms, which can facilitate the hydrogenation of N* sites. The MoCx can be a good catalyst for NRA by regulating the coordination environment of Mo atoms.

Ultrathin CoO@NC nanosheets derived from NaBH4-treated ZIF-67 for ofloxacin degradation

Modulating the morphology of precursor can effectively adjust the property of derived composite. Herein, after post-treated by NaBH4, a layered ZIF-67 precursor was endowed with high porosities, partially delaminated and curled layers. With this material as precursor, the pyrolysis composite, P-CoO@NC, exhibits a morphology of ultrathin N-doped carbon (NC) nanosheets coupled with highly dispersed CoO nanoparticles. This composite can active peroxymonosulfate (PMS) and degrade ofloxacin (OFL) with an efficiency of 96.8 % (10 min). After recycling for five times, the degradation efficiency can still reach 82.5 %, which demonstrates its catalytic activity and stability as an advance oxidation process (AOP) catalyst. As confirmed by related experiments, both radical (SO4— and O2—) and non-radical (1O2) pathways take part in OFL degradation in P-CoO@NC system. Overall, this work demonstrates a specific role of NaBH4 in modulating MOF precursor and further the property of derived composite.

CuCeOx/CuO Catalyst Derived from the Layered Double Hydroxide Precursor: Catalytic Performance in NO Reduction with CO in the Presence of Water and Oxygen.

Valencies of metal species and lattice defects, such as oxygen vacancies, play a pivotal role in metal oxide-catalyzed reactions. Herein, we report a promising synthetic strategy for preparing CuO-supported CuCeOx catalysts (CuCeOx/CuO) by calcination of a hydrotalcite precursor [Cu6Ce2(OH)16]CO3·nH2O. The structural and chemical properties of catalysts were characterized by XRD, ICP-AES, TEM, TPR, NH3-TPD, XPS, Raman spectroscopy, and N2 adsorption, which revealed that the thermal pretreatment in an oxidative atmosphere caused segregation and reconstitution processes of the precursor, resulting in a mesoporous catalyst consisting of well-dispersed CuO-supported CuCeOx clusters of 1.8-3.2 nm in size with a high population of oxygen vacancies. The as-prepared catalyst shows excellent catalytic performance in the reduction of NO by CO in the absence as well as in the presence of water and oxygen. This behavior is attributed to its high oxygen defect concentration facilitating the interplay of the redox equilibria between Cu2+ and reduced copper species (Cu+/Cu0) and (Ce4+/Ce3+). The high surface population of oxygen vacancies and in situ-generated metallic copper species have been evidenced by Raman spectroscopy and X-ray photoelectron spectroscopy. The layered double hydroxide-derived CuCeOx/CuO also showed good water tolerance and long-term stability. In situ infrared spectroscopy investigations indicated that adsorbed hyponitrite species are the main reaction intermediates of the NO conversion as also corroborated by theoretical simulations.

Scalable Synthesis of 2D Mo2 C and Thickness-Dependent Hydrogen Evolution on Its Basal Plane and Edges.

2D transition metal carbides (2D TMCs and MXenes) are promising candidates for applications of energy storage and catalysis. However, producing high-quality, large 2D flakes of Mo2C MXene has been challenging. Here, a new salt-assisted templating approach is reported that enables the direct synthesis of 2D Mo2 C with low defect concentrations. KCl acts as a template to form an intermediate 2D product, facilitating Mo2 C formation without coarsening upon melting. The thickness of the flakes produced can range from monolayer (0.36 nm) to 10 layers (4.55 nm), and the electrocatalytical hydrogen evolution reaction (HER) activity of 2D Mo2 C is inversely proportional to its thickness. The monolayer Mo2 C shows remarkable HER performance with a current density of ≈6800 mA cm- 2 at 470 mV versus reversible hydrogen electrode and an ultrahigh turnover frequency of ≈17 500 s- 1 . This salt-assisted synthesis approach can also produce WC and V8 C7 nanosheets, expanding the family of 2D carbides. The new pathway eliminates the need for layered ceramic precursors, making it a versatile approach to direct synthesis of MXene-like 2D carbides.

Engineering high-coordinated cerium single-atom sites on carbon nitride nanosheets for efficient photocatalytic amine oxidation and water splitting into hydrogen

Developing highly-active rare-earth single atom photocatalysts have attracted extensive attention due to their excellent catalytic properties. Herein, we prepared a single-atom Ce-SA-C3N4 catalyst composed of atomically dispersed rare-earth cerium (Ce) on C3N4 nanosheets by the pyrolysis of cerium-incorporated layered precursor. The atomic distribution and high-coordinated environment of Ce sites were disclosed by aberration-corrected scanning transmission electron microscopy, electron energy-loss spectra, X-ray absorption spectroscopy, and theoretical calculations. In Ce-SA-C3N4, Ce single atoms are coordinated by four N atoms and six O atoms (Ce-N4/O6). The cooperation of single-atom Ce-N4/O6 active sites in C3N4 nanosheets tunes the electronic structure and the surface trap states, resulting in accelerated charge transfer/separation and extended lifetime of photoinduced electrons. Meanwhile, the high-coordinated Ce-N4/O6 active sites could promote the production of superoxide radicals (•O2−) and C = N bond, thus, the optimized single-atom Ce-SA-C3N4 photocatalyst exhibits highly efficient photocatalytic oxidation of amines under visible light irradiation. Furthermore, the fabricated single-atom Ce-SA-C3N4 photocatalysts are applied to split water into hydrogen, producing the maximum hydrogen yield of 33.5 mmol h−1 g−1. The apparent quantum efficiency for hydrogen evolution achieves 32.6% at 420 nm. This study provides a guideline for rationally designing efficient high-coordinated rare-earth single-atom active sites for efficient solar energy conversion and utilization.

Metastability and Photoelectrochemical Properties of Cu2SnO3 and Cu2–xLixTiO3: Two Cu(I)-Based Oxides with Delafossite Structures

Metastable, p-type Cu(I)-based semiconductors were synthesized using cation-exchange reactions between delafossite-type layered precursors and CuCl flux, yielding Cu2SnO3 (I) and Cu2–xLixTiO3 (II, xmin ∼ 0.4). These represent the first reported crystalline semiconductors found in the Cu–Sn–O or Cu–Ti–O chemical systems (and not currently predicted within any materials databases), with their kinetic stabilization requiring a relatively low reaction temperature of ∼475 °C. Both phases crystallize in the monoclinic crystal system in the space group C2/c, exhibiting edge-shared hexagonal “MO3” (M = Sn or Ti) layers that also contain octahedrally coordinated Li(I)/Cu(I) cations. These layers are bridged by linearly coordinated Cu(I) cations. Magnetic susceptibility measurements confirm the +1 oxidation state of the copper cations. The optical band gaps were found to be indirect and to significantly red shift with the Cu(I) content, down to ∼2.31 eV for I and ∼1.46 eV for II. Electronic structure calculations show that the decreased band gaps can be attributed to a higher energy valence band derived from the filled 3d10 orbitals of the Cu(I) cations, which most notably arise from the octahedrally coordinated Cu(I) cations within the layers. Total energy calculations reveal an increasing metastability with respect to decomposition to Cu2O and SnO2 or TiO2 as a result of occupation of the intralayer sites by Cu(I) cations. In both phases, their edge-shared hexagonal layers lead to highly dispersive conduction bands and small electron effective masses of ∼0.51 me for I and ∼0.41 me for II. Polycrystalline films of both were deposited onto fluorine-doped tin oxide slides and exhibited p-type photocurrents under 100 mW cm–2 irradiation in the range of ∼50 to 250 μA cm–2. This study thus reveals new fundamental relationships between the origin of metastability in Cu(I)-oxide semiconductors, i.e., octahedral coordination, and enhanced optical and photoelectrochemical properties.

Synthesis of SiO2@MnCo2O4 core–shell nanorattles using layered double hydroxide precursors and studies on their peroxidase-like activity

The current work demonstrates a simple soft chemical approach to synthesize SiO2@MnCo2O4 core–shell nanorattles using SiO2@MnCo-LDH (layered double hydroxide) precursors.

Further Boosting Solar Cell Performance via Bandgap-Graded Ag Doping in Cu2ZnSn(S,Se)4 Solar Cells Compared to Uniform Ag Doping.

Cu2ZnSn(S,Se)4 (CZTSSe) is a hopeful substitution to commercialized Cu(In,Ga)Se2 (CIGSe) devices with similar structure and optoelectronic properties and has advantages of nontoxicity, low cost, and abundant reserves. However, the traditional flat bandgap structure of the CZTSSe absorber layer does not efficiently enhance the collection of photogenerated electrons and decrease recombination. Graded bandgap engineering toward the interfaces of CIGSe solar cells is the key to realize high-efficiency devices. In this study, we obtained (Cu1-xAgx)2ZnSn(S,Se)4 (CAZTSSe) absorber layers with high-concentration Ag doping at both ends of the absorption layer and undoped or low-concentration Ag doping in the middle part through a new miscible layered precursor method. This bandgap structure suppressed CuZn defects, delayed Fermi level pinning near the CZTSSe/CdS interface, sustained good electrical conductivity and light absorption in the middle of the absorption layer, improved the conversion efficiency of incident light, and inhibited recombination of carriers toward the Mo back electrode. In addition, we also compared the performance of undoped, uniformly Ag-doped, and V-type Ag-doped CZTSSe devices to acquire a deeper understanding of the reasons for the enhanced performance. It can be found that compared with undoping, the open-circuit voltage (Voc) of the best devices with uniform doping (x = 15%) increased from 379 to 386 mV, the fill factor (FF) increased from 44.70 to 54.14%, and the photoelectric conversion efficiency (PCE) increased from 4.63 to 6.21%. More surprisingly, the Voc of the optimal CAZTSSe devices (sample D) with Ag-graded doping was increased to 413 mV and the FF was increased to 59.63%. It also achieved an impressive PCE of 7.35%. The above results prove the importance of tuning Ag gradient doping of CZTSSe films for improving solar cell performance.

Enhanced Li-ion migration behavior in Li3V2O5 rock-salt anode via stepwise lattice tailoring

Electrode exploration with the appropriate equilibrium voltage and facile cation diffusion kinetics is the key enabler towards realizing the extreme power output of the battery formats. With the aid of the stepwise lattice tailoring, herein, we present an alternative fast-charging anode of the rock-salt lithium vanadium oxide. Specifically, the pre-insertion of polyaniline (PANI) molecules unlocks the basal plane of the layered V2O5 precursor, while subsequent Na+ doping at the octahedral sites could stabilize the lattice breathing and mitigate Li-ion diffusion barrier along the tetrahedron-octahedron-tetrahedron pathway, as confirmed by the operando X-ray diffraction and kinetics simulation. The Na0.6Li2.4V2O5@PANI//LiFePO4 full cell prototype (3 mAh cm−2) exhibits 82% capacity retention at 20 C for 2000 cycles, as well as the cycling endurance within a wider temperature range of 0-60°C. This stepwise lattice engineering strategy opens a fresh impetus of the electrode innovations for the high-power energy storage devices.

Versatile Layered Hydroxide Precursors for Generic Synthesis of Cu‐Based Materials

The ability to mix multiple elements in a structure is crucial for obtaining Cu‐based nanostructures and microstructures with desirable physicochemical properties. Precursors containing multiple metal cations, such as layered double hydroxides, have been used for the synthesis of multielement materials. However, these precursors experience difficulty containing large cations, which limits the functionalities of the derived materials. Herein, the development of Cu‐based hydroxy double salts (HDSs), versatile precursors that accommodate a broad range of metal cations with homogeneous distributions, is reported. Up to 25 different metal cations are mixed with Cu in an HDS single phase, individually and simultaneously. The HDSs further exhibit useful properties with respect to anion exchange, exfoliation, and phase transformation to metal oxides. During the metal oxide transformation process, the formed crystal structures are mainly dependent on the ionic radius of the secondary metal cations. To prove their utility as precursors, the metal oxides derived from the HDSs are tested and found that they exhibited high catalytic activities for CO oxidation. This study significantly expands the compositional and structural freedom of Cu‐based multi‐elemental materials.

Layered double hydroxide derived cobalt-iron sulfide heterostructures with enhanced reaction kinetics for use in sodium-ion batteries

Constructing a well-designed heterojunction on anodes of sodium ion batteries (SIBs) is an essential strategy for developing high-performance Na-storage devices. In this study, a CoS1.097/FeS lamellar heterostructure was built via a simple two-step hydrothermal treatment using layered double hydroxide precursors. The as-prepared sample exhibits a hydrotalcite-like intercalated structure and heterogeneous composition, which boosts the electrochemical reaction kinetics by shortening the transport distance, unifying move direction and accelerating mobility of Na+. Meanwhile, benefited from such advantages as additional active sites at surfaces, enhanced internal structure stability and relaxed stress from volume expansion etc., SIBs with as-prepared CoS1.097/FeS heterojunction anodes shows excellent sodium storage performances，including high rate capability (564.1 mAh g-1 at 10 A g-1), good the initial coulombic efficiency (80.65% at 0.5 A g-1) as well as great cyclability (543.9 mAh g-1 at 2 A g-1 after 450 cycles). Theoretical calculations based on the first principles are carried out to clarify the possible sodium storage mechanisms. The job may provide a feasible route and key technologies through structural designing and surface coating to prepare anode materials for high-performance sodium-ion batteries. It is expected that the current work can be extended to build other advanced electrode materials for various energy storage related applications.

Influence of hydrotalcite/rosasite precursors over Cu/Zn/Al mixed oxides on ethanol dehydrogenation

Cu/Zn/Al mixed oxides catalysts were obtained from their corresponding layered precursors synthesized by coprecipitation of components varying M(II)/M(III) molar ratios of 2, 3, and 4 while maintaining Cu2+/Zn2+ molar ratio at 1.0. Crystalline phases concentration in the precursors was determined by Rietveld refinement analysis. Hydrotalcite (HTLc) phase concentration decreased from 79 to 32 wt % as M(II)/M(III) molar ratio increased from 2 to 4, respectively. A constant value of M(II)/M(III) molar ratio of 1.3–1.4 was determined for HTLc formation independently of the M(II)/M(III) molar ratio used for the synthesis. The excess of M(II), Cu and Zn components, segregate as Rosasite phase. Therefore, mixed oxides with different surface properties were obtained depending on the precursor crystalline phase component. Precursor with mainly HTLc phase generates mostly a homogenous Cu/Zn/Al mixed oxide where Al atoms hinder Cu reduction. On that sample no Cu0 was detected by XPS, then, hydrogen consumption during its reduction process was related to the presence of anionic vacancies, where H2 can be heterolytically dissociated and stored in its hydric form, generating highly active hydro/dehydrogenation sites, with highest Lewis acidity. When the mixed oxides come from a precursor with mainly Rosasite phase, mixed oxides decompose into Cu0, ZnO, and Al2O3 during reduction, where metallic Cu0 acts as dehydrogenating sites during ethanol dehydrogenation to acetaldehyde. In fact, higher Cu surface concentration favors the dehydrogenation route, increasing the yield towards acetaldehyde, whereas a high Al surface concentration enhances the dehydration path increasing diethyl ether yield.