Surface Oxygen Species Research Articles

Ru/CeO2 catalyst derived from Ce-based MOF for highly efficient catalytic CO2 methanation integrated with renewable hydrogen

A series of highly ordered microporous Ce-based metal-organic frameworks (MOFs) were synthesized as the precursors for catalyst construction. The corresponding Ru catalysts were prepared by Ru impregnation on the derived CeO2 by pyrolysis of Ce-MOF, and investigated for the CH4 synthesis via CO2 hydrogenation. Among the catalysts, Ru catalyst supported on the CeO2-B derived from Ce-BDC exhibited a highly competitive efficiency for CO2 methanation, giving a CH4 selectivity of 100% with a CO2 conversion of 62% at 275 °C and 0.1 MPa, and the CH4 productivity reached 0.49 mol/(molRu·h). Characterization results revealed that more oxygen vacancies and corresponding surface oxygen species formed on the surface of CeO2-B derived from Ce-BDC caused to the stronger interaction between Ru and CeO2-B, which promoted the CO2 adsorption and hydrogenation capacity of the catalyst, resulting in its better catalytic property. In situ diffuse reflectance infrared Fourier transform (DRIFT) studies further revealed that the route of HCOO* into CH4 is a more competitive way of CO2 hydrogenation to CH4.

The effect of Fe2O3 doping on a Pt/Co3O4 catalyst for CO oxidation: Improvement of thermal stability and catalytic activity

Although Pt/Co3O4 is an active catalyst for CO oxidation, its low thermal stability may impede its application. The thermal stability and catalytic performance of Pt/Co3O4 were considerably enhanced by Fe2O3 doping. Fe2O3 doping stabilized the mesostructured material during the high-temperature treatment, and the Fe2O3-doped samples retained a larger specific surface area. The characterization results revealed that Fe2O3 doping inhibited catalyst crystallization and decomposition and the growth of catalyst grains during high-temperature calcination. The Fe2O3 doping reduced the Co-O bond strength in the surface Co3O4 lattice, increased the Co3+ ratio, and generated highly active surface oxygen species. Fe2O3 doping also facilitates CO2 desorption, which improves CO adsorption and oxidation. SO2 and NO impede CO oxidation on Pt/Fe2O3/Co3O4. This negative impact was caused by the inert species formed when SO2 or NO reacted with O2 on the catalyst, such as SO42-, HSO4-, or nitrate species, which covered the active sites.

Promotional effect of WO3 in V2O5–WO3/TiO2 on low-temperature activity in the catalytic oxidation of 1,2-dichloroethane

Transition metal oxides are promising catalysts for the degradation of chlorinated volatile organic compounds (CVOCs). However, their practical applications are limited due to their poor low-temperature (<300 °C) activity. In this study, we introduced WOx into VOx/TiO2 to modulate its redox and acidic properties. We found that the V2O5(2 wt%)–WO3(10 wt%)/TiO2 (2V10W/TiO2) catalyst exhibited a 1,2-dichloroethane (DCE) conversion of 90 % at 256 °C, which is comparable to that of Ru-based catalysts (DCE conversion of 90 % at 257–340 °C) for the oxidation of DCE. The addition of WOx into VOx/TiO2 gave rise to the formation of labile surface oxygen species and promoted interactions between V and W, which improved the reducibility, oxygen mobility, and Brønsted acidity of the 2V10W/TiO2 catalyst. These properties of 2V10W/TiO2 lowered its activation barrier for DCE oxidation and mitigated coke formation and Cl deposition on the catalyst, enhancing the low-temperature activity and long-term stability. The 2V10W/TiO2 catalyst also exhibited superior resistance to water. This study provides insights into catalytic design for balancing the redox and acidic properties in the catalytic oxidation of CVOCs.

Gadolinium-doped SrFeO3 as a highly active and stable electrode for symmetrical solid oxide fuel cells

Symmetrical solid oxide fuel cells (SSOFCs) with identical electrodes have gained interesting attention because of their simplified fabrication procedure and reduced processing costs. However, their development is limited by their electrocatalytic activity and stability of the electrode materials used. Here, we report a prototypical SrFeO3-δ-based perovskite oxide with formula GdxSr1-xFeO3-δ (GSF) as a highly effective SSOFC electrode material. It was found that A-site Gd substitution in SrFeO3-δ greatly improved its structural stability under reducing atmosphere. Furthermore, doping Gd was able to significantly enhance the electrochemical activity, achieving area-specific resistances of 0.18 Ω cm2 for the cathode and 0.003 Ω cm2 for the anode at 800 °C, respectively. The lower polarization resistance could be attributed to the abundant surface oxygen species through the Gd-doping in SrFeO3-δ. Benefiting from superior electrochemical activity and structural stability, the symmetrical cell with GSF-0.2 electrode showed reasonable stability and electrochemical performance. These results show that the developed GSF perovskite oxide may be a promising candidate as electrode material for symmetrical SOFCs.

Operando investigation of catalytic trichloroethylene combustion over metal-doped CeO2 nanorods

The remediation of chlorinated volatile organic compounds is an intractable issue for it typically requires high temperatures and generates undesirable byproducts. This work utilized a series of representative transition metals (i.e., Cr, Cu, V) to modify the morphology, surface oxygen, and acidity of the CeO2 nanorods for trichloroethylene (TCE) treatment. A spectroscopic operando DRIFT − online GCMS reactor was introduced to examine the catalytic performance and elucidate the reaction pathway. Among them, Cr-CeO2 exhibited 50 % (T50) and 90 % (T90) TCE conversions with no byproduct at 171 °C and 241 °C, respectively. The performances of Cu-CeO2 (T90 = 391 °C), V-CeO2 (T90 = 423 °C) and CeO2 (T90 = 494 °C) were inferior to Cr-CeO2 (T90 = 241 °C), with obvious C2Cl4 generated in the TCE oxidation. It reveals that TCE adsorbed on Cr-CeO2 is dechlorinated on acidic sites and oxidized to carbonate/formate intermediates by the surface oxygen then facilely to generate carbon oxides, while TCE is adsorbed as chlorinated species (CH2ClCH2O−) on the other three catalysts which occupy the surface and require higher temperature to be oxidized. The abundant medium-strong acidic sites and surface oxygen species of Cr-CeO2 nanorods are responsible for the low-temperature activation via C-Cl cleavage on acidic sites and fast oxidation of hydrocarbon intermediates in the TCE oxidation, respectively.

Investigation of catalytic methane oxidation over Ag/Co2MOx (M = Co, Ni, Cu) catalysts with varying interfacial electron transfer

Atom-doped Co3O4 catalysts loaded with Ag were examined as cost-effective catalysts for methane oxidation. The synthesized Ag/Co2NiOx catalysts exhibited distinctive surface characteristics in contrast with Ag/Co3O4 and Ag/Co2CuOx catalysts prepared using a similar method. Characterization results unveiled that Ag/Co2NiOx featured a higher presence of active surface oxygen species, lattice defects, a larger surface area, and enhanced reducibility. A methane oxidation catalytic performance followed the sequence: Ag/Co2NiOx > Ag/Co3O4 > Ag/Co2CuOx. The investigation delved into methane degradation pathways on the surfaces of three catalysts, examining their behavior under both aerobic and anaerobic atmospheres through in-situ DRIFTS analysis. Furthermore, introducing Ag showed a marked positive effect on Co-Ni mixed oxide, inducing electron transfer and a more active electron system, whereas it exhibited an inverse impact within the surface of Co-Cu mixed oxide. This work provides innovative perspectives on the development of forthcoming environmental catalysts.

Tuning the crystallinity of the MnOx catalysts to promote toluene catalytic oxidation

ABSTRACT In this paper, the MnOx catalysts with excellent toluene oxidation performance were prepared by a simple precipitation method. The physicochemical properties of the prepared MnOx catalysts were investigated by XRD, BET, H2-TPR, O2-TPD and XPS. The obtained results revealed that the crystallinity of the prepared MnOx catalysts could be effectively regulated by changing the (NH4)2CO3/Mn(NO3)2 molar ratio, and thus affecting the oxygen vacancy concentration of the prepared MnOx catalysts. The prepared MnOx-4 catalyst with the (NH4)2CO3/Mn(NO3)2 molar ratio of 4.0 had the poor crystallinity and small grain size, which effectively promoted the oxygen defects in the MnOx catalyst to be formed. At the same time, the MnOx-4 catalyst had a large specific surface area, the highest low temperature reducibility and the largest number of oxygen vacancies and surface adsorbed oxygen species, which allowed more surface oxygen species to participate in the redox reaction, and promoted the toluene deep oxidation. Therefore, when the (NH4)2CO3/Mn(NO3)2 molar ratio was 4.0, the prepared MnOx-4 catalyst exhibited an excellent toluene catalytic oxidation performance and robust catalytic stability. What’s more, the toluene oxidation conversion on the MnOx-4 catalyst reached 99% at 230°C, and the MnOx-4 catalyst showed excellent resistance to water vapour.

Unique role of silica in MOF-Derived High-Loading Palladium-on-Ceria single atom catalysts with excellent efficiency and durability

In most cases, the sintering tendency of supported metal single atoms could be attributed to the unstable structural characteristics of supports in demanding operating conditions, particularly for high-loading single-atom catalysts (SACs), ultimately resulting in deactivation. To address this issue, SiO2 is employed to enhance the structural stability of both supports and the supported Pd single atoms. SiO2 serves not only to prevent the collapse of support structures but also to promote the activation of surface oxygen species by facilitating electron transfer with the supports. This, in turn, establishes strong metal-support interactions (MSIs) to stabilize and activate atomically dispersed Pd species. Additionally, the electrons donated from Ce-O and Si-O to Pd atoms further catalyze the formation of oxygen vacancies, ultimately leading to significantly improved activity and durability in CO oxidation. Without SiO2, the instability of support structure, coupled with the weak MSIs, promotes the aggregation of Pd atoms, resulting in relatively lower catalytic activity and durability.

Low-Temperature Oxidation of Methane on Rutile TiO2(110): Identifying the Role of Surface Oxygen Species.

Understanding the microkinetic mechanism underlying photocatalytic oxidative methane (CH4) conversion is of significant importance for the successful design of efficient catalysts. Herein, CH4 photooxidation has been systematically investigated on oxidized rutile(R)-TiO2(110) at 60 K. Under 355 nm irradiation, the C-H bond activation of CH4 is accomplished by the hole-trapped dangling OTi- center rather than the hole-trapped Ob- center via the Eley-Rideal reaction pathway, producing movable CH3• radicals. Subsequently, movable CH3• radicals encounter an O/OH species to form CH3O/CH3OH species, which could further dissociate into CH2O under irradiation. However, the majority of the CH3• radical intermediate is ejected into a vacuum, which may induce radical-mediated reactions under ambient conditions. The result not only advances our knowledge about inert C-H bond activation but also provides a deep insight into the mechanism of photocatalytic CH4 conversion, which will be helpful for the successful design of efficient catalysts.

Efficient CO Oxidation using Co3O4−CeO2 Nanoparticles Supported on Resin–Based Spherical Activated Carbon with Controllable Oxygen Species

AbstractThe oxygen vacancies and surface oxygen species play pivotal roles in CO catalytic oxidation. In this study, Co3O4−CeO2 supported on resin based spherical activated carbon was fabricated and the effect of CeO2 on surface oxygen species was demonstrated through controlling various Ce contents. When Ce content was optimal (nCo : nCe=9), the maximum surface adsorbed oxygen content (60.3 %) is displayed and the catalyst achieved good CO conversion (T100=110 °C), water resistance and robust stability. DFT simulation calculation confirmed that the energy barriers of two transition states significantly decreased to 0.60 eV and 0.37 eV, respectively, with the addition of CeO2. The results indicate that the presence of CeO2 is conducive to the increasement of surface adsorbed oxygen content and optimal Co/Ce ratio is the most favorable for the CO oxidation. It is attributed to the visible decline of the energy barrier between oxygen vacancies and gas–phase oxygen at the Co3O4−CeO2 interface, and the process of oxygen vacancies replenishment could be more prone to occur at the interface. This study may provide a protocol for further improving surface species on supporting catalysts.

A noble-metal-free catalyst with MoC nanorod for low-temperature water gas shift reaction

Water gas shift (WGS) reaction is an important process to remove CO contaminant in industrial hydrogen resources. The efficient catalyst that can work at low temperature is keenly desired to achieve high CO conversion from the viewpoint of thermodynamic equilibrium. Here, we develop a noble-metal-free catalyst of MoC nanorod (MoC NR) with the dominant (200) facet for the low-temperature WGS reaction. It exhibits a high performance with ∼ 100 % CO conversion at 175 °C, better than conventional MoC with the dominant (111) facet or the commercial Cu-based catalyst. Moreover, it shows rather better stability due to the presence of the dominant (200) facet. Various characterizations demonstrate that this facet facilitates MoC NR possessing higher removal capability of surface oxygen species to enhance the stability and lower activation energy to endow higher performance compared with conventional MoC. This study provides important implications for the rational design of cost-effective catalysts for the low-temperature WGS reaction.

Gas-phase synthesis of MoO3 nanoclusters with helium-induced high energy (060) crystal facet: Enhancing oxygen adsorption for improved gas-sensing

Adsorbed oxygen species on the surface of metal oxide semiconductors (MOS) play an important role in the field of gas-sensing. However, considering the large number of possible MOS, manipulating surface oxygen species by exposing high-energy crystal facets often requires strict experimental conditions and may not be efficiently repeated for nano MOS. This poses a huge challenge to the rational design of advanced gas-sensing materials. This study explores the fabrication of MoO3 nanocluster (NC) film by cluster beam deposition. Helium (He) is co-fed with argon (Ar) into the aggregation chamber to influence the nucleation and growth of Mo NCs. This unique process facilitated the exposure of the high-energy (060) crystal facet in MoO3 during the aging phase. This exposed crystal facet greatly reduces the oxygen adsorption energy barrier and increases the adsorbed oxygen content, resulting in a significant improvement in gas-sensing performance. The study examined the impact of energetic facets on gas sensor sensitivity by using ethanol, ammonia, and toluene as target gases. The results indicate that exposing high-energy crystal facets significantly enhances sensor performance. This approach to creating NCs with high-energy crystal facets has broad potential for advancing MOS nanostructure-based gas sensors.

Designing State-of-the-Art Gas Sensors: From Fundamentals to Applications.

Gas sensors are crucial in environmental monitoring, industrial safety, and medical diagnostics. Due to the rising demand for precise and reliable gas detection, there is a rising demand for cutting-edge gas sensors that possess exceptional sensitivity, selectivity, and stability. Due to their tunable electrical properties, high-density surface-active sites, and significant surface-to-volume ratio, nanomaterials have been extensively investigated in this regard. The traditional gas sensors utilize homogeneous material for sensing where the adsorbed surface oxygen species play a vital role in their sensing activity. However, their performance for selective gas sensing is still unsatisfactory because the employed high temperature leads to the poor stability. The heterostructures nanomaterials can easily tune sensing performance and their different energy band structures, work functions, charge carrier concentration and polarity, and interfacial band alignments can be precisely designed for high-performance selective gas sensing at low temperature. In this review article, we discuss in detail the fundamentals of semiconductor gas sensing along with their mechanisms. Further, we highlight the existed challenges in semiconductor gas sensing. In addition, we review the recent advancements in semiconductor gas sensor design for applications from different perspective. Finally, the conclusion and future perspectives for improvement of the gas sensing performance are discussed.

Easy-regeneration Mn-doped ZIF-67 derivate adsorbent with ultra-high adsorption capacity for tetracycline hydrochloride in wastewater

Adsorption capacity and reusability are critical to the practical applications of metal–organic framework (MOF)-based adsorbents. In this work, an easy-regeneration ZIF-67 derivate adsorbent (Mn-ZIF-400) was synthesized by calcining the manganese-modified MOF ZIF-67 (Mn-ZIF-67) precursor at 400 °C in air for the first time. Mn-ZIF-400 reveals an ultra-high adsorption capacity for tetracycline hydrochloride (TCH) (qmax = 1191.5 mg⋅g−1 at 308 K at pH = 4) in a wide pH range (pH = 3–10) owing to its great surface area (816.2 m2⋅g−1), surface polyvalent metal ions (Co2+/Co3+, Mn2+/ Mn 3+/ Mn4+), abundant surface oxygen species (including –COOH, –OH etc.) and π-electrons from benzene-ring. The adsorption mechanism of TCH on Mn-ZIF-400 belongs to the monolayer chemisorption mainly by π-π conjugation/π-cation interactions, hydrogen/coordination bonding, and pore filling. It also can maintain high adsorption performance in an actual aqueous environment. More importantly, Mn-ZIF-400 showed enhanced water stability and reusability after modification and no obvious loss in adsorption capacity in four recycles via simple water washing, being a promising adsorbent for antibiotic elimination.

Electronic and surface structure engineering of oxygen vacancies-riched WO3 nanosheets toward highly efficient BTEX sensing

Oxygen vacancies engineering is a promising strategy to develop high-performance benzene and its homologues chemiresistive gas sensors, however, the lack of insights into relationship between electronic and surface structure with sensing performance greatly hinder the design of materials with robust sensing behavior. Herein, the oxygen vacancies-riched WO3 nanosheets with individual defect coordination environment have been successfully synthesized by finely tuning the treating temperature. The electronic and surface structure engineering of WO3 can be systematically modulated, and the optimal d-band structure as well as surface oxygen species on H-WO3-500 NSs presents the superior BTEX sensing performance with ultrahigh response (Ra/Rg = 64.15, 50.54, 58.79 and 56.26 to 50 ppm ethylbenzene, benzene, toluene and xylene, respectively), outstanding reliability (σ = 0.1) and sensing stability (φ = 0.37%). The combination of experimental and theoretical results reveals that the surface oxygen vacancies of WO3 facilitate the activation of higher mobility surface O-(ad), O2-(ad) species and the upshift of d-band center of W compared with the bulk oxygen vacancies, endowing it with robust surface reaction and dramatically enhanced sensing performance. This work presents a new strategy for designing of highly efficient gas sensors for monitoring hazardous molecules.

Promotion effect of epoxy group neighboring single-atom Cu site on acetylene hydrochlorination

Carbon materials have been used as the support for catalysts in the field of acetylene hydrochlorination, the influence of inevitable oxygen-containing moieties on the reaction is often ignored and the mechanism of the oxygen-doping structure remains ambiguous. Herein, we explored the effect of the oxygen-containing group (COC) in the support on the activity of single-atom dispersed Cu catalysts. By immersing the Cu single-atom catalyst in an alkaline solution, the epoxy species on the carbon support was cleaved to obtain a pure ether species while the Cu site was modified to a more electron-deficient state. The turnover frequency value of Cu/O-FLP catalyst with epoxy groups was 1.6-fold higher than that of alkaline treated catalyst. Our result indicated that the epoxy groups could assist adjacent single-atom Cu sites to synergistically promote the adsorption and cleavage of the reactant hydrogen chloride toward form COH and CuCl bonds, and reduce the reaction energy barrier. The presence of electron deficient Cu sites and ether species could induce competitive adsorption of the acetylene and hydrogen chloride, thereby reducing the activity of the catalyst. This study highlights the influence of surface oxygen species and the tunability of the support, providing the foundation for the fabrication of higher-activity Cu catalysts for acetylene hydrochlorination.

Hydroxy and surface oxygen effects on 5-hydroxymethylfurfural oxidation to 2,5-furandicarboxylic acid on β-MnO2: DFT, microkinetic and experiment studies.

Manganese dioxide, β-MnO2, has shown potential in catalyzing the oxidation of 5-hydroxymethylfurfural (HMF) to 2,5-furandicarboxylic acid (FDCA), a monomer of bioplastic polyethylene furanoate (PEF). Herein, the insight into the hydroxy (OH) and surface oxygen effects on the HMF-to-FDCA reaction over β-MnO2 is clarified through a comprehensive investigation using density functional theory (DFT) calculations, microkinetic modeling, and experiment. Theoretical analyses revealed that both active surface oxygen and OH species (from either base or solvent) facilitate C-H bond breaking and OH insertion, promoting the catalytic activity of β-MnO2. Microkinetic modeling demonstrated that the FFCA-to-FDCA and DFF-to-FFCA steps are the rate-limiting steps of the hydroxylated and non-hydroxylated surfaces, respectively. These theoretical results agree well with the experiment when water and dimethyl sulfoxide (DMSO) were used as solvents. In addition, the synthesized β-MnO2 catalyst showed high stability and activity, maintaining stable HMF conversion (≥99 mol%) and high FDCA yield (85-92 mol%) during continuous flow oxidation for 72 hours at pO2 of 1 MPa, 393 K and LHSV of 1 h-1. Thus, considering both hydroxy and surface oxygen species is a new strategy for enhancing the catalytic activity of Mn oxides and other metal oxide catalysts for the HMF-to-FDCA reaction.

Doping SnO2 with metal ions of varying valence states: discerning the importance of active surface oxygen species vs. acid sites for C3H8 and CO oxidation.

To elucidate the valence state effect of doping cations, Li+, Mg2+, Cr3+, Zr4+ and Nb5+ with radii similar to Sn4+ (CN = 6) were chosen to dope tetragonal SnO2. Cr3+, Zr4+ and Nb5+ can enter the SnO2 lattice to produce solid solutions, thus creating more surface defects. However, Li+ and Mg2+ can only stay on the SnO2 surface as nitrates, thus suppressing the surface defects. The rich surface defects facilitate the generation of active O2-/Oδ- and acid sites on the solid solution catalysts, hence improving the reactivity. On the solid solution catalysts active for propane combustion, several reactive intermediates can be formed, but are negligible on those with low activity. It is confirmed that for propane combustion, surface acid sites play a more vital role than active oxygen sites. Nevertheless, for CO oxidation, the active oxygen sites play a more vital role than the acid sites.

Oxygen dynamic exchange and diffusion characteristics of ZnO nanorods from 17O MAS NMR.

Interactions of ZnO nanorods with water and the dynamic migration characteristic of surface oxygen species are important in controlling its structure and catalytic properties. Here, we apply 17O solid-state NMR spectroscopy to investigate the interactions, as well as oxygen ion diffusion properties of ZnO nanorods under different conditions.

The nature of crystal facet effect of TiO2-supported Pd/Pt catalysts on selective hydrogenation of cinnamaldehyde: electron transfer process promoted by interfacial oxygen species.

Supported noble metal nanocatalysts typically exhibit strong crystal plane dependent catalytic behavior, but their working mechanism is still unclear. Herein, using anatase TiO2 with well-exposed crystal facets of {101}, {100} and {001} as a prototype support, Pd- and Pt-based supported TiO2 nanocatalysts (TiO2-Pd and TiO2-Pt) were prepared by chemical reduction with NaBH4 as reducer, and they showed a distinct metal-dependent crystal facet effect in the selective hydrogenation of cinamaldehyde (CAL). For Pd-based nanocatalysts, most Pd species on the {100} plane of TiO2 are present in the oxidized form with positive charges and unexpectedly show higher reactivity than the Pd species in the zero-valence state on the {101} and {001} planes. On the contrary, Pt species on all three crystal planes of TiO2 show zero-valence state, with relatively low conversion, but much better selectivity for hydrogenation of a CO bond than Pd-based catalysts. Well-designed experiments manipulating the stability and type of surface oxygen species confirmed that the essence of the crystal facet effect of the catalyst support actually creates a unique nanoconfined interface at the molecular level to construct a surface p-band intermediate state (PBIS), which provides a new alternative channel for surface electron transfer and consequently accelerates the reaction kinetics.