Active Lattice Oxygen Research Articles

Dual nanoparticles with rich Ni–CeO2 interfaces for efficient photothermal catalytic CO2 reduction by CH4

Reducing CO2 by CH4 (CRM) is of great significance for alleviating greenhouse effects and fuel shortages. However, the high energy consumption and low yield of fuel, as well as the deactivation of Ni based catalysts constrained its development. Herein, a novel Ni–CeO2/Al2O3 catalyst for photothermal catalytic CRM merely upon focused light irradiation was reported. Very high yield of H2 and CO (80.2 and 96.3 mmol min−1 g−1) and excellent catalytic durability were achieved. The results of UV-VIS-IR diffuse reflectance spectra and experimental test indicate that high yield of H2 and CO originates from efficient photothermal conversion and the molecular activation effect of light. More importantly, Ni–CeO2/Al2O3 exhibits better carbon deposition resistance than Ni/Al2O3. The structural characterization and experimental evidences reveal that the active lattice oxygen in CeO2 nanoparticles can be transferred to Ni nanoparticles via Ni–CeO2 interface to accelerate carbon oxidation and form oxygen vacancies. The formed oxygen vacancies can re-adsorb and activate CO2 to form new active lattice oxygen.

Multifunctional surface modification to enhance the electrochemical performance of lithium-rich manganese-based cathode materials

The preparation of high-performance lithium-rich manganese-based cathode materials (LLOs) require attention to the redox of anions and the migration of transition metals (TM) during the cycling process. In this study, Ce ion-doped Li-rich cathode coated with La0.2Ce0.8O2, which has abundant oxygen vacancies on its surface, was prepared. The presence of the oxygen storage material La0.2Ce0.8O2 can effectively absorb the irreversible oxygen generated during cycling, preventing it from reacting with the electrolyte to form thick cathode electrolyte interface (CEI) coatings. These coatings hinder the relative activity of lattice oxygen in the bulk phase, reducing the specific capacity of the material. Additionally, the 5d metal ion Ce carries a large nuclear charge, causing a 'pinning effect' when it integrates into the LLOs structure. This effect reduces thermal oscillation in the lattice, impedes TM migration during battery charging and discharging, and effectively prevents voltage decay. Results indicate that after 100 cycles at 1C and 25 °C, the surface-coated materials maintain a discharge-specific capacity of 194 mAh/g, compared to 158 mAh/g for uncoated material. Voltage decay decreased from 4.4 mV/cycle to 1.8 mV/cycle, with an ICE of 91.5 % versus the original material's 82.8 %. The modified material also exhibits improved rate performance, retaining a specific capacity of 162 mAh/g at 3C, in contrast to the original material's 123 mAh/g.

In Situ Surface Reaction for the Preparation of High-Performance Li-Rich Mn-Based Cathode Materials with Integrated Surface Functionalization.

Li-rich Mn-based cathode materials (LLOs) are often faced with problems such as low initial Coulombic efficiency (ICE), limited rate performance, voltage decay, and structural instability. Addressing these problems with a single approach is challenging. To overcome these limitations, we developed an LLO with surface functionalization using a simple fabrication method. This two-step process involved a liquid-stage NaBF4 treatment followed by an in situ chemical reaction during sintering. This reaction led to the creation of oxygen vacancies (OV), spinel structures, and doping with Na at the Li site, B at the tetrahedral interstitial spaces of O in both the transition-metal (TM) layer and Li layers as well as the octahedral interstices in the TM layer, and F at the O site. We have carried out a thorough study and employed density functional theory calculations to reveal the hidden mechanisms. The treatment not only increases the electrical conductivity but also changes the oxygen charge environment and inhibits lattice oxygen activity. Surprisingly, the B-O bond is so strong that it prevents the migration of TM within the tetrahedral interstitial spaces of O in both the TM and Li layers, hence stabilizing its structure. This bonding interaction strengthens the transition of the TM 3d and O 2p states to lower energy levels, thus causing an increase in the redox potentials. Hence, a rise in the operating voltage occurs. Of special importance, this therapy dramatically increases the ICE to 90.29% and keeps a specified capacity of 203.3 mAh/g after 100 cycles at 1C, which is an excellent capacity retention of 89.94%. This study introduces ideas and methods to tackle the challenges associated with LLOs in batteries. It also provides compelling evidence for the development of high-energy-density Li-ion batteries.

Atomic-Level Observation of Potential-Dependent Variations at the Surface of an Oxide Catalyst during Oxygen Evolution Reaction.

Understanding the intricate details of the surface atomic structure and composition of catalysts during the oxygen evolution reaction (OER) is crucial for developing catalysts with high stability in water electrolyzers. While many notable studies highlight surface amorphization and reconstruction, systematic analytical tracing of the catalyst surface as a function of overpotential remains elusive. Heteroepitaxial (001) films of chemically stable and lattice-oxygen-inactive LaCoO3 are thus utilized as a model catalyst to demonstrate a series of atomic-resolution observations of the film surface at different anodic potentials. The first key finding is that atoms at the surface are fairly dynamic even at lower overpotentials. Angstrom-scale atomic displacements within the perovskite framework are identified below a certain potential level. Another noteworthy feature is that amorphization (or paracrystallization) with no long-range order is finally induced at higher overpotentials. In particular, surface analyses consistently support that the oxidation of lattice oxygen is coupled with amorphous phase formation at the high potentials. Theoretical calculations also reveal an upward shift of oxygen 2p states toward the Fermi level, indicating enhanced lattice oxygen activation when atom displacement occurs more extensively. This study emphasizes that the degradation behavior of OER catalysts can distinctively vary depending on the overpotential level.

Structure and molecular-level transformation for oxidation of effluent organic matters by manganese oxides

As important organic components in water environments, effluent organic matters (EfOMs) from wastewater treatment plants are widely present in Mn-rich environments or engineered treatment systems. The redox interaction between manganese oxides (MnOx) and EfOMs can lead to their structural changes, which are crucial for ensuring the safety of water environments. Herein, the reactivities of MnOx with EfOMs were evaluated, and it was found that MnOx with high specific surface area, active high-valent manganese content and lattice oxygen content (i.e., amorphous MnO2) possessed stronger oxidizing ability towards EfOMs. Accompanying by EfOMs oxidation, Mn(IV) and Mn(III) were reduced into Mn(II), with Mn(III) as the significant active species. Through molecular-level transformation analysis by ultrahigh mass spectrometry (FT-ICR MS), the highly reactive compounds in EfOMs were clearly determined to be that with more aromatic and unsaturated structures, especially lignin-like compounds (the highest content in EfOMs (over 60 %)). EfOMs were oxidized by amorphous MnO2 into products with lower humification index (0.60 vs. 0.46), smaller apparent molecular weight (386.94 Da vs. 368.68 Da), and higher biodegradability (BOD5/COD: 0.12 vs. 0.78). This finding suggested that redox reactions between MnOx and EfOMs might alter their abiotic and biotic behaviors in receiving water environments.

Spatially asymmetrical copper dimer in ceria as an efficiently synergistic oxidation catalyst

Accurate and facile construction of atomically dispersed active sites is fundamentally important in heterogeneous catalysis. Herein, by applying a unique H2-He pretreatment, we successfully synthesize spatially asymmetrical dimeric Cu stabilized by CeO2. Integrated microscopic and spectroscopic characterizations, together with DFT calculations have revealed the redispersion of Cu species on CeO2 support is accompanied by the formation of Cu dimers with one Cu atom embedded into CeO2 lattice and the neighboring Cu atom supported on-top. The obtained dual-Cu atom catalyst demonstrates its general applicability in emission control scenarios or hydrogen fuel cell for automobile applications with excellent performances. Ab initio calculations reveal that such dimeric Cu sites on CeO2 promote reactant adsorption and lattice oxygen activation, owing to the synergistic effect of unique dimeric Cu structure. This work highlights the great potential of gas pretreatment in the fabrication of dual-atom catalysts, which is widely applicable to active site modulation in advanced oxidation catalysts.

Lattice Oxygen Activation through Deep Oxidation of Co4N by Jahn–Teller–Active Dopants for Improved Electrocatalytic Oxygen Evolution

AbstractTriggering the lattice oxygen oxidation mechanism is crucial for improving oxygen evolution reaction (OER) performance, because it could bypass the scaling relation limitation associated with the conventional adsorbate evolution mechanism through the direct formation of oxygen–oxygen bond. High‐valence transition metal sites are favorable for activating the lattice oxygen, but the deep oxidation of pre‐catalysts suffers from a high thermodynamic barrier. Here, taking advantage of the Jahn–Teller (J–T) distortion induced structural instability, we incorporate high‐spin Mn3+ ( ) dopant into Co4N. Mn dopants enable a surface structural transformation from Co4N to CoOOH, and finally to CoO2, as observed by various in situ spectroscopic investigations. Furthermore, the reconstructed surface on Mn‐doped Co4N triggers the lattice oxygen activation, as evidenced experimentally by pH‐dependent OER, tetramethylammonium cation adsorption and online electrochemical mass spectrometry measurements of 18O‐labelled catalysts. In general, this work not only offers the introducing J–T effect approach to regulate the structural transition, but also provides an understanding about the influence of the catalyst's electronic configuration on determining the reaction route, which may inspire the design of more efficient catalysts with activated lattice oxygen.

Lattice Oxygen Activation through Deep Oxidation of Co4N by Jahn-Teller-Active Dopants for Improved Electrocatalytic Oxygen Evolution.

Triggering the lattice oxygen oxidation mechanism is crucial for improving oxygen evolution reaction (OER) performance, because it could bypass the scaling relation limitation associated with the conventional adsorbate evolution mechanism through the direct formation of oxygen-oxygen bond. High-valence transition metal sites are favorable for activating the lattice oxygen, but the deep oxidation of pre-catalysts suffers from a high thermodynamic barrier. Here, taking advantage of the Jahn-Teller (J-T) distortion induced structural instability, we incorporate high-spin Mn3+ ( ) dopant into Co4N. Mn dopants enable a surface structural transformation from Co4N to CoOOH, and finally to CoO2, as observed by various in situ spectroscopic investigations. Furthermore, the reconstructed surface on Mn-doped Co4N triggers the lattice oxygen activation, as evidenced experimentally by pH-dependent OER, tetramethylammonium cation adsorption and online electrochemical mass spectrometry measurements of 18O-labelled catalysts. In general, this work not only offers the introducing J-T effect approach to regulate the structural transition, but also provides an understanding about the influence of the catalyst's electronic configuration on determining the reaction route, which may inspire the design of more efficient catalysts with activated lattice oxygen.

Rational Design Strategy for High-Valence Metal-Driven Electronically Modulated High-Entropy Co-Ni-Fe-Cu-Mo (Oxy)Hydroxide as Superior Multifunctional Electrocatalysts.

Creating durable and efficient multifunctional electrocatalysts capable of high current densities at low applied potentials is crucial for widespread industrial use in hydrogen production. Herein, a Co-Ni-Fe-Cu-Mo (oxy)hydroxide electrocatalyst with abundant grain boundaries on nickel foam using a scalable coating method followed by chemical precipitation is synthesized. This technique efficiently organizes hierarchical Co-Ni-Fe-Cu-Mo (oxy)hydroxide nanoparticles within ultrafine crystalline regions (<4nm), enriched with numerous grain boundaries, enhancing catalytic site density and facilitating charge and mass transfer. The resulting catalyst, structured into nanosheets enriched with grain boundaries, exhibits superior electrocatalytic activity. It achieves a reduced overpotential of 199mV at 10mAcm2 current density with a Tafel slope of 48.8mVdec1 in a 1m KOH solution, maintaining stability over 72h. Advanced analytical techniques reveal that incorporating high-valency copper and molybdenum elements significantly enhances lattice oxygen activation, attributed to weakened metal-oxygen bonds facilitating the lattice oxygen mechanism (LOM). Synchrotron radiation studies confirm a synergistic interaction among constituent elements. Furthermore, the developed high-entropy electrode demonstrates exceptional long-term stability under high current density in alkaline environments, showcasing the effectiveness of high-entropy strategies in advancing electrocatalytic materials for energy-related applications.

Boosting the removal of diesel soot particles by regulating the Pr−O strength over transition metal doped Pr6O11 catalysts

The content of active lattice oxygen and oxygen vacancies is crucial for the catalytic oxidation of soot. Herein, we adjust the Pr-O bond strength in Pr6O11 by doping several common transition metals (Mn, Fe, Co, Ni) to promote the formation of oxygen vacancies and the activation of lattice oxygen. This strategy does not compromise its crystal structure, allowing for improved catalytic performance while maintaining stability. The Mn-doped Pr6O11 catalyst shows the best soot catalytic oxidation performance. Its T50 (the temperature of soot conversion reaching 50 %) value is 396 °C under loose contact. Further characterizations and density functional theory (DFT) calculations demonstrate that PMO possesses a large specific surface area. Additionally, the weakening the strength of the Pr-O bond leaded to an increase in oxygen vacancies, which in turn enhanced the redox ability of catalyst. This work will provide a reference for the development of Pr-based catalysts for soot combustion.

Efficient photothermal mineralization of toluene over MnCo2O4 with different exposed facets: Revealing the role of oxygen vacancy and photo-/thermo- synergistic mechanism

Modulating oxygen vacancies through facet engineering is a potential strategy to enhance activity of photo-/thermo- synergistic catalysis for toluene mineralization. Hence, we synthesized MnCo2O4 catalysts with exposed {01−1} facets (MCO-R), {1−1−2} facets MCO-S), and {1−10} facets (MCO-C), in which the MCO-R with the highest oxygen vacancy concentration exhibited the highest toluene conversion (95.8 %) and CO2 yield (85.5 %) under the full-spectrum light irradiation. The results of various characterizations and DFT calculations confirmed that the oxygen vacancy could accelerate the activation of lattice oxygen and molecule oxygen, thereby enhancing the photothermal catalytic toluene activity of MnCo2O4. Meanwhile, the results of performance evaluations identified that the efficient photothermal mineralization activity of toluene was induced by the photo-/thermo- synergistic catalysis. Besides, the reaction pathway studies by In-situ DRIFTS tests revealed the key role of oxygen vacancy and photo-/thermo- synergistic effects in the reaction progress of photothermal mineralization of toluene over MnCo2O4.

Sorption-enhanced chemical looping steam reforming coupled with water splitting for syngas and H2 coproduction using waste plastic as fuel

Chemical looping is a promising technology for hydrogen production. Achieving both high purity and yield is an ongoing challenge, due to low fuel conversion and carbon deposition. In this study, a sorption-enhanced chemical looping reforming coupled with water splitting (SE-CLSR-WS) process was proposed to co-produce syngas and H2 by using waste plastic as the fuel. The Ni-doped Ca2Fe2O5 brownmillerites were designed and employed as oxygen carriers (OCs) and CO2 sorbent. The introduction of Ni leaded to lattice distortion of brownmillerite, thereby enhancing the redox activity of lattice oxygen. In fuel reactor (FR), CaO in-situ captured CO2 and shifted reaction equilibrium towards PET pyrolysis gas reforming, enhancing both syngas yield and PET conversion rates. Adhere to the surface of OCs, CaO improved cyclic performance by inhibiting agglomeration of active metals. Calcination reactor (CR) was set between FR and steam rector (SR) to in-situ desorb CO2 and remove carbon deposition, enhancing hydrogen purity in SR. When Ca2Ni0.75Fe1.25O5-0.25CaO was applied to SE-CLSR-WS process, it exhibited synergistically strengthened performance in reaction activity, sorption capacity and cyclic stability, with a syngas purity of 82.71 % and H2 yield of 8.01 mmol/g OC with 93.26 % purity.

Lattice Oxygen Activation Triggered by Ultrasonic Shock Significantly Improves NO Selective Catalytic Reduction

Lattice Oxygen Activation Triggered by Ultrasonic Shock Significantly Improves NO Selective Catalytic Reduction

Lattice-confined Ag over MnCoLDH accelerated catalytic oxidation of formaldehyde at ambient temperature: The novel pathway with different oxygen species

Catalytic oxidation of formaldehyde (HCHO) at ambient temperature represents a cost-effective and efficient strategy for indoor HCHO removal. Although precious metal-based catalysts have been considered practical for oxidizing gaseous HCHO indoors, the limited activity of Ag-based catalysts can be attributed to their typical +1 and 0 valence states, as well as their single electron transport pathway. This characteristic impedes the reestablishment of the low state during oxygen activation, thereby resulting in catalyst deactivation. The present study successfully incorporated Ag atoms into manganese-cobalt layered double hydroxide (MnCoLDH) through doping, resulting in the development of a catalyst that exhibited complete formaldehyde oxidation activity at 30 °C. Lattice-confined Ag enables continuous activation of oxygen, while LDH facilitates the sustained provision of surface hydroxyl groups. The roles and mechanisms of surface hydroxyl groups, adsorbed oxygen, and lattice oxygen in the oxidation of formaldehyde were investigated using in-situ DRIFTS. By comparing Ag with the impregnation method, the confinement of Ag within the lattice enables continuous activation of oxygen. This study presents a viable strategy for designing efficient catalysts for volatile organic compounds (VOCs) removal by utilizing active lattice oxygen species.

Enhanced reactivity over Ce2(SO4)3/MgO with NiO modification for chemical looping partial oxidation of methane

Chemical looping partial oxidation of methane to syngas is a promising process. Thermodynamic and kinetic analysis both forecast the NiO/Ce2(SO4)3–MgO is a prospective oxygen carrier (OC) to this process, which enables with 100% syngas selectivity, 2.15H2/CO ratio, excellent methane conversion and stable cycling characteristic. Compared with Ce2(SO4)3, the methane conversion rate rise by 73.19% because of the excellent lattice oxygen availability, less carbon deposit, and large specific surface area. The distinctive pore structure also provides a favorable reaction environment. Through the density functional theory, Ni doping can lower the energy barrier (Eb), promote lattice oxygen activation and diffusion, and the oxygen vacancy (Ov) can further promote these processes. CH3 → CH2 + H (TS2) is the rate-limiting step. Compared with Ce2(SO4)3, the Ni doping can reduce Eb by 16.8%, and the Ov can further reduce it by 43.0%. It does not change when the Ov concentration is more than 1.96%.

Enhanced Replenishment of Active Lattice Oxygen Using Chiral Copper Oxide.

Effective catalytic performance of the transition metal oxide is attributed to high specific surface areas, abundant surface oxygen atoms, and balanced valence ratios. Although the chirality of the transition metal has attracted attention, most studies have focused on optical application. A few chiral transition metal oxides were used as electrocatalysts and photocatalysts. The influence of the chiral catalysts on the thermal catalysis process has been less explored. In this study, Mn-loaded chiral (M/l-CuO and M/d-CuO) and achiral CuO (M/a-CuO) were synthesized and compared in the catalytic oxidization of toluene. Spectrally analyzed Mn was well-dispersed on both chiral and achiral CuO. l-CuO and d-CuO showed nanoflower-like chirality. The angles between each (001) plane of CuO were the source of chirality. The toluene turnover frequency (TOF) of the samples was in the order of Mn/d-CuO (5.6 × 10-5 s-1) > Mn/l-CuO (4.4 × 10-5 s-1) > Mn/a-CuO (3.2 × 10-5 s-1) at 240 °C, consistent with the order of the oxygen replenishment rate. The as-prepared catalysts had similar ratios of lattice oxygen/surface adsorbed oxygen, Mn3+/Mn4+, and Cu+/Cu2+. A higher TOF was attributed to chirality, which increased the lattice oxygen replenishment speed from the gaseous phase to the solid surface. Our study indicates gas-solid catalysis from a structure-activity viewpoint.

Regulating the electronic state of SnO2@NiFe-LDH heterojunction: Activating lattice oxygen for efficient oxygen evolution reaction

In Oxygen Evolution Reaction (OER), catalysts with lattice oxygen, utilizing the Lattice Oxygen Mechanism (LOM), directly participate in oxygen evolution, effectively reducing activation energy. NiFe-Layered Double Hydroxides (NiFe-LDHs), rich in surface hydroxyls, are potential for LOM. However, their stability is challenged in alkaline conditions due to metal cation dissolution from the lattice, limiting catalytic efficiency. In this work, we modify NiFe-LDH by combining hydrothermal and electrodeposition techniques, coupling NiFe-LDH with the metal oxide SnO2. This process creates a heterojunction enriched with oxygen vacancies through interfacial and defect engineering. In 1 M KOH solution, this modified catalyst exhibits an OER overpotential of just 209 mV at a current density of 10 mA cm−2. Furthermore, when the current density is increased to 100 mA cm−2, the overpotential only increases by a modest 46 mV. Subsequent DFT investigations reveal that in the heterostructured system, there is an enhanced overlap between the O 2p and metal 3d orbitals, which optimizes the covalency of the metal–oxygen bond and promotes the participation of lattice oxygen in the reduction reaction. The heterojunction, in concert with oxygen vacancies, aligns the energy bands of oxygen and metal closer to the Fermi level, resulting in improved continuity of electronic orbitals near the Fermi level. This synergistic arrangement significantly reduces the energy barrier for the rate-determining step of the OER, substantiating the improved performance and activation of lattice oxygen.

Modulating the Electronic Structures of Pt on Pt/TiO2 Catalyst for Boosting Toluene Oxidation.

Surface hydroxyl groups commonly exist on the catalyst and present a significant role in the catalytic reaction. Considering the lack of systematical researches on the effect of the surface hydroxyl group on reactant molecule activation, the PtOx/TiO2 and PtOx-y(OH)y/TiO2 catalysts were constructed and studied for a comprehensive understanding of the roles of the surface hydroxyl group in the oxidation of volatiles organic compounds. The PtOx/TiO2 formed by a simple treatment with nitric acid presented greatly enhanced activity for toluene oxidation in which the turnover frequency of toluene oxidation on PtOx/TiO2 was around 14 times as high as that on PtOx-y(OH)y/TiO2. Experimental and theoretical results indicated that adsorption/activation of toluene and reactivity of oxygen atom on the catalyst determined the toluene oxidation on the catalyst. The removal of surface hydroxyl groups on PtOx promoted strong electronic coupling of the Pt 5d orbital in PtOx and C 2p orbital in toluene, facilitating the electron transfers from toluene to PtOx and subsequently the adsorption/activation of toluene. Additionally, the weak Pt-O bond promoted the activation of surface lattice oxygen, accelerating the deep oxidation of activated toluene. This study clarifies the inhibiting effect of surface hydroxyl groups on PtOx in toluene oxidation, providing a further understanding of hydrocarbon oxidation.

Tuning benzene activity of cobalt-based spinel catalysts with cation substitution

Cobalt-based spinel oxides are promising low-cost catalysts for volatile organic compounds (VOCs) elimination. Herein, we prepared the cobalt-based spinel oxides (MCo2O4: M = Ni, Cu, Co, Zn) by a one-step solvothermal method to evaluate the influence of cation substitution on benzene combustion. The cation distribution on tetrahedral and octahedral sites could influence the degree of inversion in cobalt-based spinel oxides, thus achieving the regulation of Co-O bond strength. NiCo2O4 catalyst with the inverse spinel structure had the weak Co-O bond strength, which is conducive to the activation of lattice oxygen to improve the activity of benzene degradation. This work provides deep insights into the influence of the cation substitution on the cobalt-based spinel catalysts for the efficient benzene oxidation.

Morphology engineering of Co3O4 spinel for efficient oxidation of lean methane at low temperature

Nowadays, the development of high-performance non-noble metal catalysts is an important research direction for controlling methane emissions from liquefied natural gas (LNG)-powered vehicles and vessels, and Co3O4 spinel has attracted great attention. In this work, Co3O4 catalysts with different morphologies (flower, sheet, particle, and cube) were synthesized by hydrothermal method and their catalytic performance was evaluated. The results showed that the flower-like Co3O4 (Co3O4-F) catalyst exhibited the highest activity in the lean methane oxidation with the T90 (temperature at the methane conversion of 90%) of 365 °C. Compared to other catalysts, Co3O4-F contained an amount of Co3+ sites and the weakest Co3+-O bond, which facilitated the extraction of active lattice oxygen and the initial oxidation of methane to intermediate products (formate and -COO-) on the catalyst surface. Meanwhile, the abundant oxygen vacancies on the surface of the Co3O4 catalyst could efficient activate O2 to form active oxygen species, which promoted the oxidation of intermediate products to CO2 and H2O. The methane oxidation over the Co3O4-F was confirmed to conform with Mars-van Krevelen mechanism. This work provides a facile way to enhance the methane oxidation activity of Co3O4 catalysts by modulating the morphology.