Atomic‐Scale CoOx Species in Metal–Organic Frameworks for Oxygen Evolution Reaction

The activity of electrocatalysts strongly depends on the number of active sites, which can be increased by downsizing electrocatalysts. Single‐atom catalysts have attracted special attention due to atomic‐scale active sites. However, it is a huge challenge to obtain atomic‐scale CoO_x catalysts. The Co‐based metal–organic frameworks (MOFs) own atomically dispersed Co ions, which motivates to design a possible pathway to partially on‐site transform these Co ions to active atomic‐scale CoO_x species, while reserving the highly porous features of MOFs. In this work, for the first time, the targeted on‐site formation of atomic‐scale CoO_x species is realized in ZIF‐67 by O₂ plasma. The abundant pores in ZIF‐67 provide channels for O₂ plasma to activate the Co ions in MOFs to on‐site produce atomic‐scale CoO_x species, which act as the active sites to catalyze the oxygen evolution reaction with an even better activity than RuO₂.     

Thermoelectric Properties of Na<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>CoO<Subscript>2</Subscript> and Prospects for Other Oxide Thermoelectrics

We discuss the thermoelectric properties of Na _x CoO₂ using the electronic structure, as determined in first principles calculations, and Boltzmann kinetic transport theory. The Fermi energy lies near the top of a manifold of Co t _2g bands. These t _2g bands are separated by a large gap from the higher-lying e _g states. Although the large crystal-field splitting implies substantial Co–O hybridization, the bands are narrow. Application of standard Boltzmann transport theory to such a narrow band structure yields high thermopowers in accord with experimental observations, even for high metallic carrier densities. The high thermopowers observed for Na _x CoO₂ can therefore be explained by standard band theory and do not rely on low dimensionality or correlation effects specific to Co. We also present results for the cubic spinel structure ZnRh₂O₄. Like Na _x CoO₂, this compound has very narrow valence bands. We find that if it could be doped with mobile carriers, it would also have a high thermopower, comparable with that of Na _x CoO₂.     

Activating Both Basal Plane and Edge Sites of Layered Cobalt Oxides for Boosted Water Oxidation

Layered A_xCoO₂ materials built by stacking layers of CoO₂ slabs and inserting alkali ions in between them have shown a promising activity of oxygen evolution reaction (OER) due to their active edge sites. However, the large basal plane areas of the CoO₂ slabs show too strong adsorption energy to the reaction intermediates, which is unfavorable for the release of O₂. Here, a simple cation-exchange strategy based on Fe³⁺ and alkali ions is proposed to simultaneously activate both the basal plane and edge sites of A_xCoO₂ for the OER. X-ray absorption spectroscopy has revealed that the Fe³⁺ ions deposit both on the surface and edge sites of the CoO₂ slabs and enter the interlayer. The cation-exchanged A_xCoO₂ electrodes show a boosted activity compared to their pristine and conventional Fe-doped A_xCoO₂ counterparts. This phenomenon is mainly ascribed to the abundant edge-sharing Co–Fe motifs at the edge sites and the charge redistribution in the basal plane sites induced by the insertion of Fe³⁺ ions. This work provides a novel method to fully exploit layer-structured materials for efficient energy conversion.     

Effects of Pulsed Laser Deposition Conditions on the Microstructure of Ca<Subscript>3</Subscript>Co<Subscript>4</Subscript>O<Subscript>9</Subscript> Thin Films

The influence of deposition conditions on the microstructure of Ca₃Co₄O₉ (CCO) thin films fabricated by the pulsed laser deposition technique was investigated. X-ray diffraction revealed that a fast deposition rate resulted in not only low crystallinity but also the existence of the Ca _x CoO₂ secondary phase. The Ca _x CoO₂ structure was further confirmed by high-resolution transmission electron microscopy. The CCO thin-film growth was deduced to be a kinetically controlled process, and the quality of the thin films strongly depended on the coalescence process. The formation of Ca _x CoO₂ was inevitable during the thin-film growth. However, given enough time and supply of oxygen at a lower deposition rate, it was possible to transform the Ca _x CoO₂ phase into the desired CCO phase during the coalescence process, while with faster deposition, more Ca _x CoO₂ structure was formed, and the secondary phase could hardly transform into the CCO phase.     

Hollow Multishelled Structure of Heterogeneous Co3O4–CeO2−x Nanocomposite for CO Catalytic Oxidation

Herein, hollow multishelled structure (HoMS) of Co₃O₄–CeO_2?x nanocomposites with controllable molar ratio of Co and Ce elements is synthesized by a general strategy sequential templating approach (STA) with a facile and efficient electrostatic spray process. As a catalyst of carbon monoxide (CO) catalytic oxidation, Co₃O₄–CeO_2?x (Co/Ce = 4/1) HoMS achieves good catalytic activity (complete conversion temperature is 166.9 °C) and stability (100 h). This performance is attributed to synergistic effects between the two components. The combination of Co₃O₄ and CeO₂ not only generates more interfaces of Co₃O₄–CeO_2?x, which is more favorable for the activation of oxygen, but also improves the oxidizability of Co₃O₄ as well as the capacity of oxygen storage of CeO₂. In addition, the relatively larger effective specific surface area of the HoMS can provide more active sites, while the unique structure of HoMS can facilitate gas diffusion and maintain structural stability.     

On the Excess Oxygen in Four-Layered Rock-Salt-Type Units of Modulated Thermoelectric Bi-Sr-(Co,Rh)-O Compounds

Excess oxygen exists in four-layered rock-salt (RS)-type units of modulated misfit-layered Bi-Sr-(Co,Rh)-O compounds, which consist of interpenetrating CdI₂-type (Co,Rh)O₂ and distorted four-layered RS-type block subsystems, which have two b-axes, i.e., b ₁ and b ₂, respectively. From carefully determined chemical contents and misfit ratios, p = b ₁/b ₂, two structural characteristics are concluded, namely, intermixing metal ions in the RS-type layers and excess oxygen δ in, or in the vicinity of, them. The chemical formulae are proposed as [(Bi_1−x (Co,Rh) _x )₂(Sr_1−y Bi _y )₂O_4+δ ] _p (Co,Rh)O₂. The valence states of␣cobalt and rhodium ions are close to 3.3+. These valence states are quite reasonable for good thermoelectric oxides, such as γ-Na_0.7CoO₂ and [Ca₂CoO₃]_0.62CoO₂. Excess oxygen would cause the undulated atomic arrangement.     

Substitutionally Dispersed High-Oxidation CoOx Clusters in the Lattice of Rutile TiO2 Triggering Efficient Co?Ti Cooperative Catalytic Centers for Oxygen Evolution Reactions

The development of economical, highly active, and robust electrocatalysts for oxygen evolution reaction (OER) is one of the major obstacles for producing affordable water splitting systems and metal-air batteries. Herein, it is reported that the subnanometric CoO_x clusters with high oxidation state substitutionally dispersed in the lattice of rutile TiO₂ support (Co-TiO₂) can be prepared by a thermally induced phase segregation process. Owing to the strong interaction of CoO_x clusters and TiO₂ support, Co-TiO₂ exhibits both excellent intrinsic activity and durability for OER. The turnover frequency of Co-TiO₂ is up to 3.250 s⁻¹ at overpotentials of 350 mV; this value is one of the highest in terms of OER performance among the current Co-based active materials under similar testing conditions; moreover, the OER current density loss is only 6.5% at a constant overpotential of 400 mV for 30 000 s, which is superior to the benchmark Co₃O₄ and RuO₂ catalysts. Mechanism analysis demonstrates that charge transfer occurs between Co sites and their neighboring Ti atoms, triggering the efficient Co Ti cooperative catalytic centers, in which OH* and O* are preferred to be adsorbed on the bridging sites of Co and Ti with favorable adsorption energy, inducing a lower energy barrier for O₂ generation.     

Anti‐Oxygen Leaking LiCoO2

LiCoO₂ is a prime example of widely used cathodes that suffer from the structural/thermal instability issues that lead to the release of their lattice oxygen under nonequilibrium conditions and safety concerns in Li‐ion batteries. Here, it is shown that an atomically thin layer of reduced graphene oxide can suppress oxygen release from Li_xCoO₂ particles and improve their structural stability. Electrochemical cycling, differential electrochemical mass spectroscopy, differential scanning calorimetry, and in situ heating transmission electron microscopy are performed to characterize the effectiveness of the graphene‐coating on the abusive tolerance of Li_xCoO₂. Electrochemical cycling mass spectroscopy results suggest that oxygen release is hindered at high cutoff voltage cycling when the cathode is coated with reduced graphene oxide. Thermal analysis, in situ heating transmission electron microscopy, and electron energy loss spectroscopy results show that the reduction of Co species from the graphene‐coated samples is delayed when compared with bare cathodes. Finally, density functional theory and ab initio molecular dynamics calculations show that the rGO layers could suppress O₂ formation more effectively due to the strong C? O_cathode bond formation at the interface of rGO/LCO where low coordination oxygens exist. This investigation uncovers a reliable approach for hindering the oxygen release reaction and improving the thermal stability of battery cathodes.     

Self-Standing Nanofiber Electrodes with Pt–Co Derived from Electrospun Zeolitic Imidazolate Framework for High Temperature PEM Fuel Cells

Expedited conversion of O₂ to H₂O with minimal amounts of Pt is essential for wide applicability of PEM fuel cells (PEMFCs). Therefore, it is imperative to develop a process for catalyst management to circumvent unnecessary catalyst loss while improving the Pt utilization, catalytic activity, and durability. Here, the fabrication of a self-standing nanofiber electrode is demonstrated by employing electrospinning. This film-type catalyst simultaneously contains Pt–Co alloy nanoparticles and Co embedded in an N-doped graphitized carbon (Co–N_x) support derived from the electrospun zeolitic imidazolate frameworks. Notably, the flexible electrode is directly transferrable for the membrane-electrode assembly of high temperature PEMFC. In addition, the electrodes exhibit excellent performance, maybe owing to the synergistic interaction between the Pt–Co and Co–N_x as revealed by the computational modeling study. This method simplifies the fabrication and operation of cell device with negligible Pt loss, compared to ink-based conventional catalyst coating methods.     

Oxygen Vacancies Modified TiO2/O-Terminated Ti3C2 Composites: Unravelling the Dual Effects between Oxygen Vacancy and High-Work-Function Titanium Carbide

The rational design of Ti₃C₂T_x MXene-derived TiO₂-based photocatalysts with broad light absorption and efficient charge separation has recently attracted considerable attention for antibiotic degradation. However, the complementary effects of each component, especially oxygen vacancies (OVs) and high work function O-terminated Ti₃C₂ (O-Ti₃C₂), in affecting light absorption and photocatalytic activity remain controversial. In this study, Ti₃C₂T_x-derived TiO₂/Ti₃C₂T_x photocatalysts are regulated by alkalization in the controlled KOH solution and calcination in different heating atmospheres to reveal the contribution of OVs, Ti³⁺, carbon species, and high work function titanium carbide. Carbon species and rich OVs co-exist in TiO₂/O-Ti₃C₂ (OV/C-TT-1K(N₂)) which exhibit superior photocatalytic performance in tetracycline hydrochloride degradation with a kinetic constant of 0.0217 min⁻¹. Combined with experimental and DFT computational results, the broadened visible light response and desirable redox properties are caused by OVs and carbon dopants, as well as decreased Schottky barrier height and enhanced electronic conductivity caused by high work function O-Ti₃C₂.     

Hybrid Catalyst Coupling Zn Single Atoms and CuNx Clusters for Synergetic Catalytic Reduction of CO2

Reverse water-gas shift (RWGS) reaction is the initial and necessary step of CO₂ hydrogenation to high value-added products, and regulating the selectivity of CO is still a fundamental challenge. In the present study, an efficient catalyst (CuZnN_x@C-N) composed by Zn single atoms and Cu clusters stabilized by nitrogen sites is reported. It contains saturated four-coordinate Zn-N₄ sites and low valence CuN_x clusters. Monodisperse Zn induces the aggregation of pyridinic N to form Zn-N₄ and N₄ structures, which show strong Lewis basicity and has strong adsorption for *CO₂ and *COOH intermediates, but weak adsorption for *CO, thus greatly improves the CO₂ conversion and CO selectivity. The catalyst calcined at 700 °C exhibits the highest CO₂ conversion of 43.6% under atmospheric pressure, which is 18.33 times of Cu-ZnO and close to the thermodynamic equilibrium conversion rate (49.9%) of CO₂. In the catalytic process, CuN_x not only adsorbs and activates H₂, but also cooperates with the adjacent Zn-N₄ and N₄ structures to jointly activate CO₂ molecules and further promotes the hydrogenation of CO₂. This synergistic mechanism will provide new insights for developing efficient hydrogenation catalysts.     

Heterogeneous,Porous 2D Oxide Sheets via Rapid Galvanic Replacement: Toward Superior HCHO Sensing Application

2D heterogeneous oxide nanosheets (NSs) have attracted much attention in various scientific fields owing to their exceptional physicochemical properties. However, the fabrication of 2D oxide NSs with abundant p–n interfaces and large amounts of mesopores is extremely challenging. Here, a facile synthesis of highly porous 2D heterogeneous oxide NSs (e.g., SnO₂/CoO_x) is suggested through a 2D oxide exfoliation approach combined with a fast galvanic replacement reaction (GRR). The ultrathin (<5 nm) layered CoO_x NSs are simply prepared by ion‐exchange exfoliation and a subsequent GRR process that induces a rapid phase transition from p‐type CoO_x to n‐type SnO₂ metal oxides (<10 min). The controlled GRR process enables the creation of heterogeneous SnO₂/CoO_x NSs consisting of small SnO₂ grain sizes (<10 nm), high porosity, numerous heterojunctions, and sub‐10 nm thickness, which are highly advantageous characteristics for chemiresistive sensors. Due to the advantage of these features, the porous SnO₂/CoO_x NSs exhibit an unparalleled HCHO‐sensing performance (R_air/R_gas > 35 @ 5 ppm with a response speed of 9.34 s) with exceptional selectivity compared to that of the state‐of‐the‐art metal oxide‐based HCHO gas sensors.     

Promoting Active Sites in Core–Shell Nanowire Array as Mott–Schottky Electrocatalysts for Efficient and Stable Overall Water Splitting

Developing earth‐abundant, active, and robust electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a vital challenge for efficient conversion of sustainable energy sources. Herein, metal–semiconductor hybrids are reported with metallic nanoalloys on various defective oxide nanowire arrays (Cu/CuO_x, Co/CoO_x, and CuCo/CuCoO_x) as typical Mott–Schottky electrocatalysts. To build the highway of continuous electron transport between metals and semiconductors, nitrogen‐doped carbon (NC) has been implanted on metal–semiconductor nanowire array as core–shell conductive architecture. As expected, NC/CuCo/CuCoO_x nanowires arrays, as integrated Mott–Schottky electrocatalysts, present an overpotential of 112 mV at 10 mA cm^?2 and a low Tafel slope of 55 mV dec^?1 for HER, simultaneously delivering an overpotential of 190 mV at 10 mA cm^?2 for OER. Most importantly, NC/CuCo/CuCoO_x architectures, as both the anode and the cathode for overall water splitting, exhibit a current density of 10 mA cm^?2 at a cell voltage of 1.53 V with excellent stability due to high conductivity, large active surface area, abundant active sites, and the continuous electron transport from prominent synergetic effect among metal, semiconductor, and nitrogen‐doped carbon. This work represents an avenue to design and develop efficient and stable Mott–Schottky bifunctional electrocatalysts for promising energy conversion.     

Nanocasting of Mesoporous In‐TM (TM = Co,Fe, Mn) Oxides: Towards 3D Diluted‐Oxide Magnetic Semiconductor Architectures

Transition metal (Co, Fe, Mn)‐doped In₂O_3?y mesoporous oxides are synthesized by nanocasting using mesoporous silica as hard templates. 3D ordered mesoporous replicas are obtained after silica removal in the case of the In‐Co and In‐Fe oxide powders. During the conversion of metal nitrates into the target mixed oxides, Co, Fe, and Mn ions enter the lattice of the In₂O₃ bixbyite phase via isovalent or heterovalent cation substitution, leading to a reduction in the cell parameter. In turn, non‐negligible amounts of oxygen vacancies are also present, as evidenced from Rietveld refinements of the X‐ray diffraction patterns. In addition to (In_1?xTM_x)₂O_3?y, minor amounts of Co₃O₄, α‐Fe₂O₃, and Mn_xO_y phases are also detected, which originate from the remaining TM cations not forming part of the bixbyite lattice. The resulting TM‐doped In₂O_3?y mesoporous materials show a ferromagnetic response at room temperature, superimposed on a paramagnetic background. Conversely, undoped In₂O_3?y exhibits a mixed diamagnetic‐ferromagnetic behavior with much smaller magnetization. The influence of the oxygen vacancies and the doping elements on the magnetic properties of these materials is discussed. Due to their 3D mesostructural geometrical arrangement and their room‐temperature ferromagnetic behavior, mesoporous oxide‐diluted magnetic semiconductors may become smart materials for the implementation of advanced components in spintronic nanodevices.     

Size‐Controlled Synthesis of Cu2‐xE (E = S,Se) Nanocrystals with Strong Tunable Near‐Infrared Localized Surface Plasmon Resonance and High Conductivity in Thin Films

A facile method for preparing highly self‐doped Cu_2‐xE (E = S, Se) nanocrystals (NCs) with controlled size in the range of 2.8–13.5 nm and 7.2–16.5 nm, for Cu_2‐xS and Cu_2‐xSe, respectively, is demonstrated. Strong near‐infrared localized surface plasmon resonance absorption is observed in the NCs, indicating that the as‐prepared particles are heavily p‐doped. The NIR plasmonic absorption is tuned by varying the amount of oleic acid used in synthesis. This effect is attributed to a reduction in the number of free carriers through surface interaction of the deprotonated carboxyl functional group of oleic acid with the NCs. This approach provides a new pathway to control both the size and the cationic deficiency of Cu_2‐xSe and Cu_2‐xS NCs. The high electrical conductivity exhibited by these NPs in metal‐semiconductor‐metal thin film devices shows promise for applications in printable field‐effect transistors and microelectronic devices.     

Separated Active Site and Reaction Space for Multi-Pollutant Elimination Significantly Enhancing Low Toxic Product Selectivity

It is possible to remove volatile organic compounds containing chlorine (CVOCs, such as chlorobenzene) in a single device designed for selective catalytic reduction of NO_x with NH₃ for the industries containing CVOCs and NO_x. Breaking the efficiency-selectivity trade-off in chlorobenzene oxidation remains a major challenge due to the conjugation of halogen atoms with the benzene ring and the reducing nature of NH₃. A stepwise synthesis strategy is demontrated to disperse dual Ru/Cu Lewis acid sites outside and inside the zeolite channel. Under the confinement of zeolite, the Ru⁴⁺ Lewis acid site on the external surface of the zeolite promotes chlorobenzene oxidation by weakening the p-π conjugate structure of Cl and benzene ring, while the Cu²⁺ Lewis acid site within the internal channel converts NO_x and NH₃ to N₂. The mutual interference between catalytic oxidation and reduction is successfully avoided. Therefore, the low toxic CO₂ and HCl selectivity experience a considerable increase from 21% to 86%, and from 51% to 94% with 91% conversion of chlorobenzene, while maintaining excellent elimination performance for NO (with N₂ selectivity exceeding 90%). The incorporation of separated active sites and reaction spaces into the design may offer potentials for other energy and environmental applications.     

Evidence that N2O is a stronger oxidizing agent than O2 for both Ta2O5 and bare Si below 1000 °C and temperature for minimum low-K interfacial oxide for high-K dielectric on Si

N₂O is known to be the stronger oxidizing agent than O₂ for the post-deposition annealing of Ta₂O₅·N₂O should also be stronger than O₂ for Si oxidation. However, NO released from N₂O is also a nitridation agent which can produce silicon oxynitride at a temperature above 1000 °C and silicon oxynitride can be a diffusion barrier for oxygen. Below 1000 °C, SiO sublimation can make the comparison of N₂O oxidation and O₂ oxidation of Si difficult. Below 750 °C, N₂O is obviously the faster oxidizing agent than O₂ for bare Si. Furthermore, our results show that minimum interfacial SiO_x, which has a low dielectric constant, occurs at about 800 °C or 950 °C for high-K metallic oxide gate insulator for future generations of CMOS because rapid thermal oxidation at these two temperatures can help to reduce leakage current or charge trapping by suppressing oxygen vacancies without too much low-K interfacial SiO_x formation.     

PbSe/PbS and PbSe/PbSexS1–x Core/Shell Nanocrystals

The synthesis of PbSe/PbS and PbSe/PbSe_xS_1–x core/shell nanocrystals (NCs) with luminescence quantum efficiencies of 45–55 % is reported. PbSe/PbS NCs are prepared via a two‐stage process, while the PbSe/PbSe_xS_1–x NCs are formed in a single‐stage procedure. The core/shell NCs exhibit an energy tuning of the exciton transitions, with respect to that of the core NC, that is dependent on the core diameter, shell thickness, and composition.     

Influence of the deposition parameters on the growth of SiGe nanocrystals embedded in Al2O3 matrix

Si_1−xGe_x nanocrystals (NCs), embedded in Al₂O₃ matrix, were fabricated on Si (100) substrates by RF-magnetron sputtering technique with following annealing procedure at 800 °C, in nitrogen atmosphere. The presence of Si_1−xGe_x NCs was confirmed by grazing incidence X-ray diffraction (GIXRD), grazing incidence small angle X-ray scattering (GISAXS) and Raman spectroscopy. The influence of the growth conditions on the structural properties and composition of Si_1−xGe_x NCs inside the alumina matrix was analyzed. Optimal conditions to grow Si_1−xGe_x (x∼ 0.8) NCs sized between 3 and 4 nm in Al₂O₃ matrix were established.     

High-Loading Co Single Atoms and Clusters Active Sites toward Enhanced Electrocatalysis of Oxygen Reduction Reaction for High-Performance Zn–Air Battery

The development of precious-metal alternative electrocatalysts for oxygen reduction reaction (ORR) is highly desired for a variety of fuel cells, and single atom catalysts (SACs) have been envisaged to be the promising choice. However, there remains challenges in the synthesis of high metal loading SACs (>5 wt.%), thus limiting their electrocatalytic performance. Herein, a facile self-sacrificing template strategy is developed for fabricating Co single atoms along with Co atomic clusters co-anchored on porous-rich nitrogen-doped graphene (Co SAs/AC@NG), which is implemented by the pyrolysis of dicyandiamide with the formation of layered g-C₃N₄ as sacrificed templates, providing rich anchoring sites to achieve high Co loading up to 14.0 wt.% in Co SAs/AC@NG. Experiments combined with density functional theory calculations reveal that the co-existence of Co single atoms and clusters with underlying nitrogen doped carbon in the optimized Co₄₀SAs/AC@NG synergistically contributes to the enhanced electrocatalysis for ORR, which outperforms the state-of-the-art Pt/C catalysts with presenting a high half-wave potential (E_1/2 = 0.890 V) and robust long-term stability. Moreover, the Co₄₀SAs/AC@NG presents excellent performance in Zn–air battery with a high-peak power density (221 mW cm⁻²) and strong cycling stability, demonstrating great potential for energy storage applications.