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Electrochemistry and X-ray absorption spectroscopy (XAS) of MnO2/reduced graphene oxide (RGO) were made to evaluate capacitive performance and electronic structure as a supercapacitor. MnO2 was deposited on the surface of RGO by a spontaneous redox reaction. At low current density (1 A g−1), the specific capacitance of MnO2/RGO (MRGO) greatly increased with increasing growth time from 281 to 462 F g−1. Electrochemical results show that the specific capacitance of RGO and MRGO arises from the combined contributions of electrochemical double-layer capacitance (EDLC) and pseudo-capacitance. To gain insights into the charge storage mechanism of RGO and MRGO, it was characterized using ex-situ soft XAS techniques at Mn L-edge and C, O K-edges in the charging/discharging process. The ex-situ soft XAS results provide evidence that the contribution of RGO to specific capacitance involves an oxygen-functionality-related contribution of pseudocapacitance and EDLC. In addition, the specific capacitance of MRGO reveals pseudocapacitive contributions from the redox processes that involve the Mn(III)/Mn(IV) redox reaction in MnO2. This work utilizes electrochemical and ex-situ XAS techniques to elucidate charge storage mechanism for supercapacitor applications.

Electro-oxidation of 5-hydroxymethylfurfural (HMFOR) is a promising green approach to realize the conversion of biomass into value-added chemicals. However, considering the complexity of the molecular structure of HMF, an in-depth understanding of the electrocatalytic behavior of HMFOR has rarely been investigated. Herein, the electrocatalytic mechanism of HMFOR on nickel nitride (Ni3N) is elucidated by operando X-ray absorption spectroscopy (XAS), in situ Raman, quasi in situ X-ray photoelectron spectroscopy (XPS), and operando electrochemical impedance spectroscopy (EIS), respectively. The activity origin is proved to be Ni2+δN(OH)ads generated by the adsorbed hydroxyl group. Moreover, HMFOR on Ni3N relates to a two-step reaction: Initially, the applied potential drives Ni atoms to lose electrons and adsorb OH− after 1.35 VRHE, giving rise to Ni2+δN(OH)ads with the electrophilic oxygen; then Ni2+δN(OH)ads seizes protons and electrons from HMF and leaves as H2O spontaneously. Furthermore, the high electrolyte alkalinity favors the HMFOR process due to the increased active species (Ni2+δN(OH)ads) and the enhanced adsorption of HMF on the Ni3N surface. This work could provide an in-depth understanding of the electrocatalytic mechanism of HMFOR on Ni3N and demonstrate the alkalinity effect of the electrolyte on the electrocatalytic performance of HMFOR.

High-entropy alloys (HEAs) have been widely studied due to their unconventional compositions and unique physicochemical properties for various applications. Herein, for the first time, we propose a surface strain strategy to tune the electrocatalytic activity of HEAs for methanol oxidation reaction (MOR). High-resolution aberration-corrected scanning transmission electron microscopy (STEM) and elemental mapping demonstrate both uniform atomic dispersion and the formation of a face-centered cubic (FCC) crystalline structure in PtFeCoNiCu HEAs. The HEAs obtained by heat treatment at 700°C (HEA-700) exhibit 0.94% compressive strain compared with that obtained at 400°C (HEA-400). As expected, the specific activity and mass activity of HEA-700 is higher than that of HEA-400 and most of the state-of-the-art catalysts. The enhanced MOR activity can be attributed to a shorter Pt-Pt bond distance in HEA-700 resulting from compressive strain. The nonprecious metal atoms in the core could generate compressive strain and down shift d-band centers via electron transfer to surface Pt layer. This work presents a new perspective for the design of high-performance HEAs electrocatalysts.

Photocatalytic overall water splitting can be achieved using Z-scheme systems that mimic natural photosynthesis by combining dissimilar semiconductors in series. However, coupling well-suited H2- and O2-evolving components remains challenging. Here, we fabricate a Z-scheme system for photocatalytic overall water splitting based on boron-doped, nitrogen-deficient carbon nitride two-dimensional (2D) nanosheets. We prepare ultrathin carbon nitride nanosheets with varying levels of boron dopants and nitrogen defects, which leads to nanosheets that can act as either H2- or O2-evolving photocatalysts. Using an electrostatic self-assembly strategy, the nanosheets are coupled to obtain a 2D/2D polymeric heterostructure. Owing to their ultrathin nanostructures, strong interfacial interaction and staggered band alignment, a Z-scheme route for efficient charge-carrier separation and transfer is realized. The obtained heterostructure achieves stoichiometric H2 and O2 evolution in the presence of Pt and Co(OH)2 co-catalysts, and the solar-to-hydrogen efficiency reaches 1.16% under one-sun illumination. Splitting water using suspensions of particulate carbon nitride-based photocatalysts may be a cheap way to produce hydrogen, but efficiencies have remained low. Now, Shen and colleagues use doped carbon nitride-based Z-scheme heterostructures to split water with a solar-to-hydrogen efficiency of 1.1% in the presence of metal-based co-catalysts.

Li-CO2 batteries have recently attracted attention as promising candidates for next-generation energy storage devices due to their extremely high theoretical energy density. The real application of Li-CO2 cells involves addressing several drawbacks, including high charging potential, poor coulombic efficiency, and low rechargeability. Molybdenum disulfide supported on carbon nanotubes (MoS2/CNT) with various ratios functioned as a cathode catalyst for Li-CO2 batteries. The optimal MoS2/CNT composite achieved a maximum discharge capacity of 8551 mAh g-1 with a coulombic efficiency of 96.7%. This hybrid also obtained an initial charging plateau of 3.87 V at a current density of 100 mA g-1 with a cutoff capacity of 500 mAh g-1. It provided ideal electrochemical stability of 142 cycles at the current densities of 100 mA g-1, which was comparable with that of some precious metal catalysts. This optimized MoS2/CNT was also cycled at 200 and 400 mA g-1 for 112 and 55 times, respectively. Density functional theory calculations demonstrated that the sulfided Mo-edge (s-Mo-edge) on MoS2 materials showed appropriate adsorption strengths of Li, CO2, and Li2CO3. Moreover, joint results of Raman profiles and extended X-ray absorption fine structure spectra elucidated that the catalytic efficiencies of MoS2/CNT hybrids were proportional to the quantities of exposed s-Mo-edge active sites.

Oxygen evolution reaction (OER) is a bottleneck process for many electrochemical devices due to the sluggish kinetics, for which advanced electrocatalysts should be carefully designed. Nickle-based materials have been extensively studied to catalyze OER. However, their performances are still below the expectation and the active sites are often controversial. Herein, we have successfully modulated the electronic and surface properties of layered •-Ni(OH)2 by the interlayer ligand engineering, aiming to design novel efficient electrocatalysts and unveil the catalysis mechanism. By one-step solvothermal reaction, alkoxyl substituted •-Ni(OH)2 with variable interlayer distances is obtained, and the ethoxyl substituted one (NiEt) shows great potential for efficient OER. With the assistance of powder X-ray diffraction and crystalline structure computational simulation, the formula of alkoxyl substituted •-Ni(OH)2 are determined. Operando X-ray absorption spectroscopy studies combined with ex-situ analyses revealed that the critical active species of NiEt is formed via hydroxylation and subsequent de-protonation, with high valent Niδ+ (3

Ni-based electrocatalysts with strong redox abilities are active for the electrochemical oxidation of 5-hydroxymethylfurfural (HMF). Interface engineering is an efficient way to modulate the electronic structure, tune the intermediate adsorption, and expose more active sites. Herein, we increased the concentration of interfacial sites with rich defects in a 3D hierarchical nanostructured NiO-Co3O4 electrocatalyst and investigated its catalytic performance for HMF electro-oxidation. The interface effect created abundant cation vacancies, modulated the electronic properties of Co and Ni atoms, and raised the oxidation state of Ni species. The NiO-Co3O4 catalysts show superb HMF oxidation activities with a low onset potential of 1.28 VRHE. Meanwhile, in-situ surface-selective vibrational spectroscopy of sum-frequency generation was performed to study the reaction pathway during the oxidation process on the electrocatalysts. The current study offers an efficient way to create cation vacancies and proves the decisive role of cation vacancies in catalyzing the HMF electro-oxidation.

Controllable design and synthesis of catalysts with the target active sites are extremely important for their applications such as for the oxygen reduction reaction (ORR) in fuel cells. However, the controllably synthesizing electrocatalysts with a single type of active site still remains a grand challenge. In this study, we developed a facile and scalable method for fabricating highly efficient ORR electrocatalysts with sole atomic Fe–N4 species as the active site. Herein, the use of cost‐effective highly porous carbon as the support not only could avoid the aggregation of the atomic Fe species but also a feasible approach to reduce the catalyst cost. The obtained atomic Fe–N4 in activated carbon (aFe@AC) shows excellent ORR activity. Its half‐wave potential is 59 mV more negative but 47 mV more positive than that of the commercial Pt/C in acidic and alkaline electrolytes, respectively. The full cell performance test results show that the aFe@AC sample is a promising candidate for direct methanol fuel cells. This study provides a general method to prepare catalysts with a certain type of active site and definite numbers.

Superoxide (LiO2) formation on charging is one of the major causes of poor cycle life of Li–O2 batteries. The underlying mechanism controlling LiO2 formation remains elusive. Here, we reveal that t...

The electronic structure of layered double hydroxides (LDHs) can be modulated by heteroatom doping and creating vacancies. The number of exposed active sites can be enriched by exfoliating the bulk structure into fewer layers. Herein, we successfully achieved multielement doping and exfoliation for Co3Fe LDHs by one SF6-plasma etching step at room temperature (named as Co3Fe LDHs-SF6). The obtained Co3Fe LDHs-SF6 ultrathin nanosheets display outstanding oxygen evolution reaction (OER) activity, which only needs 268 mV overpotential to reach 10 mA cm-2. Tafel slope and charge transfer resistance are dramatically decreased indicating a faster reaction kinetic rate. The excellent OER activity can be attributed to an increased number of active sites and an optimized electronic structure modulated by the incorporation of electron-withdrawing F, electron-donating S, and abundant vacancies resulting in proper adsorption energy to oxygen species.

The SrTiO3 thin films were fabricated by pulsed laser deposition. Subsequently ion implantation with 60 keV N ions at two different fluences 1 × 1016 and 5 × 1016 ions/cm2 and followed by annealing was carried out. Thin films were then characterized for electronic structure, morphology and transport properties. X-ray absorption spectroscopy reveals the local distortion of TiO6 octahedra and introduction of oxygen vacancies due to N implantation. The electrical and thermoelectric properties of these films were measured as a function of temperature to understand the conduction and scattering mechanisms. It is observed that the electrical conductivity and Seebeck coefficient (S) of these films are significantly enhanced for higher N ion fluence. The temperature dependent electrical resistivity has been analysed in the temperature range of 80–400 K, using various conduction mechanisms and fitted with band conduction, near neighbour hopping (NNH) and variable range hopping (VRH) models. It is revealed that the band conduction mechanism dominates at high temperature regime and in low temperature regime, there is a crossover between NNH and VRH. The S has been analysed using the relaxation time approximation model and dispersive transport mechanism in the temperature range of 300–400 K. Due to improvement in electrical conductivity and thermopower, the power factor is enhanced to 15 µWm−1 K−2 at 400 K at the higher ion fluence which is in the order of ten times higher as compared to the pristine films. This study suggests that ion beam can be used as an effective technique to selectively alter the electrical transport properties of oxide thermoelectric materials.

Metal phosphates are considered as advanced electrocatalysts for oxygen evolution reaction in metal-air batteries and water splitting devices. However, it is of huge challenge to expose more active sites due to the typical amorphous feature. Besides, proper defect engineering is promising to enhance the performance of electrocatalysts. Herein, we have successfully prepared disordered CoFePi nanosheets with rich vacancies from layered double hydroxide by a solution plasma method. The plasma can etch the interlayer anions to realize the physical exfoliation of layered double hydroxides. Meanwhile, the as-physically-exfoliated layered double hydroxides nanosheets are in-situ chemically-conversed to disordered CoFePi nanosheets by the NaH2PO4. The X-ray adsorption spectra results suggest the abundance of vacancies in the products. Cobalt tends to adjust the local structural rearrangement and to sustain the structure in the presence of a great deal of oxygen and metal vacancies. Under this adjustment, the crystal field is expected to be influenced in CoFePi. The oxygen and metal vacancies may be extensively present in MO6 octahedra layers, giving rise to a relative structure disorder and more unbonded speciec within the layers which provides more active sites in CoFePi. As a result, the disordered CoFePi nanosheets with rich vacancies could catalyse OER effectively.

In this work we propose a study to determine the structure of Fe and Co doped TiO2 by using the Fe K-edge, Co K-edge and Ti K- edge X-ray absorption near edge spectroscopy. The detailed analysis of Fe and Co-doped TiO2 before and after Methylene blue (MB) treatment was examined under the irradiation of 35 W xenon arc lamp for 3 h. The materials treated with MB were studied by X-ray absorption spectroscopy, EPR and FT-IR which revealed that the oxidation state of Co2+ was photo-oxidized to Co3+ and Fe3+ was photo-reduced to Fe2+ or less. Thermodynamic, kinetic properties were studied at different reaction temperature and the activation energy (Ea), enthalpy (ΔH), entropy (ΔS) and free energy (ΔG) of activation were calculated for the reaction. The activation energy has been found for TiO2, Fe TiO2 and Co TiO2 as 24.771, 11.413 and 15.801 kJ mol−1 respectively. The structure, morphology and optical properties were studied by XRD, UV-diffuse reflectance spectra, FESEM, TEM and PL. Moreover, electrochemical studies were carried out to demonstrate the oxygen evolution reaction (OER) activity on TiO2, Fe TiO2 and Co TiO2 in 1 M of H2SO4 electrolyte, with a scan rate of 50 mV s−1 and the as-prepared photocatalysts could act as the promising electrode materials for water splitting.

Electrochemical and ex-situ X-ray absorption spectroscopic (XAS) measurements of NiCo2O4 that have been annealed in different gases (Ar and air) were made to evaluate the efficiency of its electrocatalysis of hydrogen generation by the electrolysis of urea. The electrochemical and XAS measurements demonstrated that NCO–Ar contain significant amounts of Co2+ in octahedral coordination was more favorable than NCO-air for urea electrolysis owing to the effective exposure of electrochemical active sites to participate in the Faradic redox reaction. Further insight into the electrocatalytic mechanism of NiCo2O4-based materials during urea electrolysis was obtained using ex-situ soft XAS. The results of ex-situ soft XAS revealed that the variation of the octahedral and tetrahedral coordinations of Co2+ in NCO–Ar and NCO-air importantly contributes to electrocatalytic behavior. NCO–Ar exhibits excellent electrocatalytic activity towards the Co redox couples in a repetitive cycling process owing to the creation of highly efficient active sites (octahedral Co2+). This study presents importantly x-ray spectroscopic determination of the change in electronic structure of catalyst for hydrogen production.

Recently, a novel rechargeable Al ion battery (AIB) with high performance has been developed. Owing to its low cost, high-rate capability, excellent cyclability, and non-flammability, AIB provides a safe alternative to many commercial batteries used in the energy storage system. To improve its performance, identifying molecular structure and arrangement of chloroaluminate anion (AlCl4−) intercalated in the graphite layer remains a great challenge. In this work, operando analysis of X-ray diffraction (XRD) measurement and X-ray absorption (XAS) spectroscopy were performed to investigate the intercalation of AlCl4− anion and related molecular arrangement in the graphite layers. The intercalated stage and intercalant gallery height of graphite cathode electrode during AIB battery operation were observed to be stage 3 and 9.22 A, respectively. Furthermore, the spectral evolution from ex-situ XAS at the Al and Cl K-edge was associated with closely packed intercalation of AlCl4− molecules. With density functional theory (DFT) calculation, three simulated models of intercalated AlCl4− molecules in the graphite layer were revealed successfully, which explained possible molecular structures at different charging states. This analytical methodology paves the way for better understanding the structural transformation of molecular ions de-/intercalation in graphite layers.

In the present study, thin films of single-phase CoSb3 were deposited onto Si(100) substrates via pulsed laser deposition (PLD) method using a polycrystalline target of CoSb3. These films were implanted by 120 keV Fe-ions with three different fluences: 1 × 1015, 2.5 × 1015 and 5 × 1015 ions per cm2. All films were characterised by X-ray diffraction (XRD), Raman spectroscopy, atomic force microscopy (AFM), Rutherford backscattering (RBS) spectrometry and X-ray absorption spectroscopy (XAS). XRD data revealed that the ion implantation decreased the crystalline nature of these films, which are recovered after the rapid thermal annealing process. The Seebeck coefficient S vary with the fluences in the temperature range of 300 K to 420 K, and is found to be highest (i.e., 254 μV K−1) at 420 K for the film implanted with 1 × 1015 ions per cm2. The high S and low resistivity lead to the highest power factor for the film implanted with 1 × 1015 ions per cm2 (i.e., 700 μW m−1 K−2) at 420 K. The changing of the sign of S from negative for the pristine film to positive for the Fe-implanted samples confirm that the Fe ions are electrically active and act as electron acceptors by replacing the Co atoms. XAS measurements confirm that the Fe ions occupied the Co site in the cubic frame of the skutterudite and exist in the 3+ oxidation state in this structure.

Herein, we effectively modulate the electronic structure of Co3Fe layered double hydroxides (LDHs) by F-doping using a CHF3-plasma etching technique. CHF3-plasma can selectively fill oxygen vacancies with F− ions that can drastically tune the electronic structure with the highest electronegativity and create metal vacancies at the same time. The as-obtained F-Co3Fe LDH ultrathin nanosheets exhibit excellent oxygen evolution reaction (OER) properties. The outstanding electrochemical activity can be attributed to the incorporation of F− ions that strongly modulate the charge distribution of surrounding atoms to facilitate the adsorption of OER intermediates. This work provides a simple way to create metal vacancies and selectively fill oxygen vacancies with fluorine at the same time, and brings about a deep understanding of the electronic environment-activity relationship of LDHs for the OER.

The interface between Pt nanoparticles and support materials is of critical importance for tuning the electrocatalytic properties. The physical and chemical characteristics of metal oxide would influence the electronic and physical interactions with Pt nanoparticles. Engineering the interface interaction between Pt and CeO2 may be an effective way to modulate the electrocatalytic activity for electro-oxidation of methanol (MOR). Herein, ceria nanorods with rich oxygen vacancies (Vo) and rough surface have been induced by plasma surface engineering, and used as Pt support. For the special property of ceria, the particle size and dispersion of Pt nanoparticles could be well modified, the interaction of Pt and ceria are also regulated. Interestingly, the abundant Vo on ceria surface afford surplus electrons, which would transfer to the sub-surface with decreased Ce valence in the sub-surface of CeO2, and change the electron transfer between Pt and ceria, increase the electron density of Pt. Due to unique electron structure of Pt and CeO2, MOR catalytic activity and durability of the electrocatalyst are significantly enhanced.

The present study utilizes synchrotron-based x-ray diffraction (XRD), photoluminescence (PL), and x-ray absorption near edge structure (XANES) spectroscopic techniques to comprehend the evolution of optical intense blue-green emission in 100 keV nitrogen (N) ion implanted $\mathrm{Sr}\mathrm{Ti}{\mathrm{O}}_{3}$ (STO) thin films deposited by RF magnetron sputtering technique. The XRD pattern shows a shift in reflections at lower N ion fluences and the amorphization of the films at higher fluences. A disordered phase induced by implantation in the STO films leads to an intense blue-green emission due to oxygen (O) vacancies and N ($2p$) bound states. A schematic diagram of energy levels has been proposed to explain the origin of PL emission. The XANES spectra at Ti $K$ edge reflect a change in the valency of Ti ions and the local atomic structure of ordered and disordered phases of STO with an increase in N ion fluence. The splitting of peak assigned to ${e}_{g}$ orbitals, and discrepancy in ratio ${d}_{{z}^{2}}/{d}_{{x}^{2}\ensuremath{-}{y}^{2}}$ observed in the Ti $L$- and O $K$-edge spectra, confirm a distortion in $\mathrm{Ti}{\mathrm{O}}_{6}$ octahedral structure and modifications in O $2p$-Ti $3d$ hybridization states. The synchrotron-based techniques reveal that N ion implanted STO can be a good photoluminescent material exhibiting a variety of emissions through bound states of O vacancies and implanted N ions.

The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (nos. 51961165103 and 51672210) and the National Key Research and Development Program of China (2018YFB1502003 and 2017YFE0193900). S.S. is supported by the National Program for Support of Top-notch Young Professionals and “The Youth Innovation Team of Shaanxi Universities.”

Self-passivation in aqueous solution and sluggish surface reaction kinetics significantly limit the photoelectrochemical (PEC) performances of silicon-based photoelectrodes. Herein, a WO3 thin layer is deposited on the p-Si substrate by pulsed laser deposition (PLD), acting as a photocathode for PEC hydrogen generation. Compared to bare p-Si, the single-junctional p-Si/WO3 photoelectrodes exhibit excellent and stable PEC performances with significantly increased cathodic photocurrent density and exceptional anodic shift in onset potential for water reduction. It is revealed that the WO3 layer could reduce the charge transfer resistance across the electrode/electrolyte interface by eliminating the effect of Fermi level pinning on the surface of p-Si. More importantly, by varying the oxygen pressures during PLD, the collaborative modulation of W-O bond covalency and WO6 octahedral structure symmetry contributes to the promoted charge carrier transport and separation. Meanwhile, a large band bending at the p-Si/WO3 junction, induced by the optimized O vacancy contents in WO3, could provide a photovoltage as high as ∼ 500 mV to efficiently drive charge transfer to overcome the water reduction overpotential. Synergistically, by manipulating W-O local atomic structures in the deposited WO3 layer, a great improvement in PEC performance could be achieved over the single-junctional p-Si/WO3 photocathodes for solar hydrogen generation.

Nickel–iron composites are efficient in catalyzing oxygen evolution. Here, we develop a microorganism corrosion approach to construct nickel–iron hydroxides. The anaerobic sulfate-reducing bacteria, using sulfate as the electron acceptor, play a significant role in the formation of iron sulfide decorated nickel–iron hydroxides, which exhibit excellent electrocatalytic performance for oxygen evolution. Experimental and theoretical investigations suggest that the synergistic effect between oxyhydroxides and sulfide species accounts for the high activity. This microorganism corrosion strategy not only provides efficient candidate electrocatalysts but also bridges traditional corrosion engineering and emerging electrochemical energy technologies., Developing facile strategies to realize the precise construction of Ni-Fe structures is of significance for water oxidation. Here, the authors demonstrate a universal microorganism-assisted corrosion strategy for preparing highly efficient Ni-Fe composites towards oxygen evolution.

Ion leaching from pure-phase oxygen-evolving electrocatalysts generally exists, leading to the collapse and loss of catalyst crystalline matrix. Here, different from previous design methodologies of pure-phase perovskites, we introduce soluble BaCl2 and SrCl2 into perovskites through a self-assembly process aimed at simultaneously tuning dual cation/anion leaching effects and optimizing ion match in perovskites to protect the crystalline matrix. As a proof-of-concept, self-assembled hybrid Ba0.35Sr0.65Co0.8Fe0.2O3-δ (BSCF) nanocomposite (with BaCl2 and SrCl2) exhibits the low overpotential of 260 mV at 10 mA cm-2 in 0.1 M KOH. Multiple operando spectroscopic techniques reveal that the pre-leaching of soluble compounds lowers the difference of interfacial ion concentrations and thus endows the host phase in hybrid BSCF with abundant time and space to form stable edge/face-sharing surface structures. These self-optimized crystalline structures show stable lattice oxygen active sites and short reaction pathways between Co–Co/Fe metal active sites to trigger favorable adsorption of OH− species., Water oxidation catalysis may provide the electrons needed for sustainable fuel production, but catalysts often degrade under working conditions. Here, authors introduce soluble species into perovskites to exert positive ion leaching effects for enhancing perovskite stability and activity.

The ability to determine the electronic structure of catalysts during electrochemical reactions is highly important for identification of the active sites and the reaction mechanism. Here we successfully applied soft X-ray spectroscopy to follow in operando the valence and spin state of the Co ions in Li2Co2O4 under oxygen evolution reaction (OER) conditions. We have observed that a substantial fraction of the Co ions undergo a voltage-dependent and time-dependent valence state transition from Co3+ to Co4+ accompanied by spontaneous delithiation, whereas the edge-shared Co–O network and spin state of the Co ions remain unchanged. Density functional theory calculations indicate that the highly oxidized Co4+ site, rather than the Co3+ site or the oxygen vacancy site, is mainly responsible for the high OER activity., Determining catalyst electronic structures during electrochemical reactions is crucial to understand mechanisms. Here authors perform in operando soft X-ray spectroscopy on a cobalt oxide catalyst during O2 evolution and observe voltage and time-dependent valence state transitions.

Nonnoble metal catalysts are low-cost alternatives to Pt for the oxygen reduction reactions (ORRs), which have been studied for various applications in electrocatalytic systems. Among them, transition metal complexes, characterized by a redox-active single-metal-atom with biomimetic ligands, such as pyrolyzed cobalt–nitrogen–carbon (Co–Nx/C), have attracted considerable attention. Therefore, we reported the ORR mechanism of pyrolyzed Vitamin B12 using operando X-ray absorption spectroscopy coupled with electrochemical impedance spectroscopy, which enables operando monitoring of the oxygen binding site on the metal center. Our results revealed the preferential adsorption of oxygen at the Co2+ center, with end-on coordination forming a Co2+-oxo species. Furthermore, the charge transfer mechanism between the catalyst and reactant enables further Co–O species formation. These experimental findings, corroborated with first-principle calculations, provide insight into metal active-site geometry and structural evolution during ORR, which could be used for developing material design strategies for high-performance electrocatalysts for fuel cell applications., Understanding active-site geometry and structural evolution during electrocatalysis is important for further development. Here the authors use operando X-ray absorption spectroscopy combined with electrochemical impedance spectroscopy to investigate single atom catalysts derived from Vitamin B12.

In the synthesis of CuInS2 quantum dots (QDs), the halide ions present in the copper salts influence the QD growth and optical properties. X-ray absorption spectroscopy allowed rationalizing the halide incorporation in the lattice and the dependence of electronic properties of the material on the ion's polarizability and interaction with hydrophobic moieties.

Direct formic acid fuel cell (DFAFC) has been considered as a promising energy conversion device for stationary and mobile applications. Advanced platinum (Pt) electrocatalysts for formic acid oxidation reaction (FAOR) are critical for DFAFC. However, the oxidation of formic acid on Pt catalysts often occurs via a dual pathway mechanism, which hinders the catalytic activity owing to the CO poisoning. Herein, we directly exfoliate bulk antimony to 2D antimonene (Sb) and in situ load Pt nanoparticles onto antimonene sheets with the assistance of ethylenediamine. According to the Bader charge analysis, the charge transfer from antimonene to Pt occurs, confirming the electronic interaction between Pt and Sb. Interestingly, antimonene, as a cocatalyst, alters the oxidation pathway for FAOR over Pt catalyst and makes FAOR follow the more efficient dehydrogenation pathway. The density functional theory (DFT) calculation demonstrates that antimonene can activate Pt to be a lower oxidative state and facilitate the oxidation of HCOOH into CO 2 via a direct pathway, resulting in a weakened intermediate binding strength and better CO tolerance for FAOR. The specific activity of FAOR on Pt/Sb is 4.5 times, and the mass activity is 2.6 times higher than the conventional Pt/C.

The present study reports the effect of Ni ion implantation on the structural, compositional, electrical, and thermoelectric properties and electronic structures of CoSb3 skutterudite thin films deposited on Si substrate by pulsed laser deposition. Ni ions were implanted at 200 keV in CoSb3 thin films at three different fluences: 3 × 1015, 6 × 1015, and 1.5 × 1016 ions/cm2. X-ray diffraction of Ni-implanted films shows an additional phase of Co0.75Ni0.25Sb3. The electrical measurement of pristine films exhibits typical semiconductor behavior, while the Ni-implanted films show an abrupt increase in resistivity, which may be attributed to the formation of Co0.75Ni0.25Sb3 and material modification by the energetic ion beam. The Seebeck coefficient measurements imply that all the films are n-type with maximum Seebeck coefficient of ∼75 μV/K at ∼410 K for 2% Ni-implanted film which is about 7 times higher than the pristine CoSb3 film. The X-ray absorption study of Ni, Co, and Sb spectrum confirms that Ni ions ...

Designing atomically dispersed metal catalysts for oxygen reduction reaction (ORR) is a promising approach to achieve efficient energy conversion. Herein, we develop a template-assisted method to synthesize a series of single metal atoms anchored on porous N,S-codoped carbon (NSC) matrix as highly efficient ORR catalysts to investigate the correlation between the structure and their catalytic performance. The structure analysis indicates that an identical synthesis method results in distinguished structural differences between Fe-centered single-atom catalyst (Fe-SAs/NSC) and Co-centered/Ni-centered single-atom catalysts (Co-SAs/NSC and Ni-SAs/NSC) because of the different trends of each metal ion in forming a complex with the N,S-containing precursor during the initial synthesis process. The Fe-SAs/NSC mainly consists of a well-dispersed FeN4S2 center site where S atoms form bonds with the N atoms. The S atoms in Co-SAs/NSC and Ni-SAs/NSC, on the other hand, form metal-S bonds, resulting in CoN3S1 and NiN3S1 center sites. Density functional theory (DFT) reveals that the FeN4S2 center site is more active than the CoN3S1 and NiN3S1 sites, due to the higher charge density, lower energy barriers of the intermediates, and products involved. The experimental results indicate that all three single-atom catalysts could contribute high ORR electrochemical performances, while Fe-SAs/NSC exhibits the highest of all, which is even better than commercial Pt/C. Furthermore, Fe-SAs/NSC also displays high methanol tolerance as compared to commercial Pt/C and high stability up to 5000 cycles. This work provides insights into the rational design of the definitive structure of single-atom catalysts with tunable electrocatalytic activities for efficient energy conversion.

The oxygen evolution reaction (OER) is an ideal model to study the relationship between the activity and the surface properties of catalysts. Defect engineering has been extensively developed to tune the electrocatalytic activity for OER. Compared to the anion vacancies in metal oxides, cation vacancies are more challenging to selectively generate, and the insight into the structure and activity of cation vacancies-rich catalysts are lacked. Herein, using SnCoFe perovskite hydroxide as a precursor, abundant Sn vacancies on the surface were preferentially produced by Ar plasma. Sn vacancies could be preferentially produced as confirmed by the X-ray absorption spectra, probably owing to the lower lattice energy and weaker chemical bonds of Sn(OH)4 . The Sn vacancies promoted the exposure of active CoFe sites, resulting in an amorphous surface layer, modulated the conductivity, and thus enhanced the OER performance.

We report on the synthesis, and structural – magnetic characterizations of Mn doped Bi2Se3 towards achieving a magnetically doped topological insulator. High quality single crystals of MnxBi2−xSe3 (x = 0, 0.03, 0.05, 0.1) are grown and analysed by X-ray diffraction (XRD), Low Energy Electron Diffraction (LEED), Scanning electron microscopy (SEM), and X-ray absorption near-edge structure spectroscopy (XANES). Magnetic properties of these samples under ZFC-FC protocol and isothermal magnetization confirm ferromagnetic correlation above x = 0.03 value. XANES measurements confirm that the dopant Mn is in Mn2+ state. This is further reconfirmed to be in high spin state by fitting magnetic data with Brillouin function for J = 5/2. Both Hall and Seebeck measurements indicate a sign change of charge carriers above x = 0.03 value of Mn doping. We propose Mn doped Bi2Se3 to be a potential candidate for electromagnetic and thermoelectric device applications involving topological surface states.

We report the contribution of oxygen vacancies for enhancing the optical and visible photocatalytic properties of Cu-doped CeO2 nanoparticles (NPs) synthesized through a low-temperature coprecipitation method. Doping Cu ions in the ceria lattice in different mole percentages, 0, 3, 5, 7, 9, and 15 wt %, results in enhancement of visible photocatalytic properties even under natural sunlight. Transmission electron microscopy and X-ray diffraction studies showcase the monodispersive nature of Cu-doped CeO2 NPs in the size range of 3–7 nm with face-centered cubic structure. The Cu-based defect states induce a narrow band function in ceria nanostructures and influence the red shift in absorption with the Cu concentrations. Visible photocatalytic degradation of methylene blue was investigated in the presence of pure CeO2 NPs, CuO NPs, and Cu-doped CeO2 NPs. These studies revealed that the 7 wt % of Cu-doped CeO2 NPs exhibit the degradation rates of 1.41 × 10–2 and 1.12 × 10–2 min–1 under exposure to natural sun...

Plasmonic photocatalyst of Au nanoparticle-decorated hollow mesoporous TiO2 with 0, 0.1, 0.25, 0.5, and 1% Au content was successfully synthesized by a hydrothermal method. Controlling the particle size of Au coated on TiO2 hollow microspheres (AuTHMSs) is expected to improve the photocatalytic ability. Our results of X-ray absorption spectroscopy (XAS) indicated that the coated Au ions are nulvalent and cause a lattice distortion as well as a variation in Ti 3d orbital orientation. It is also inferred that TiO6 octahedral symmetry is significantly affected by the Au incorporation, giving rise to an increase in the Ti 3d t2g unoccupied state. UV–visible absorption spectra and I–V measurements were performed to examine localized surface plasmon resonance (LSPR) effect and photoelectrocatalytic (PEC) ability. We present the first in situ XAS measurements on AuTHMS system, which enabled us to correlate the electronic structure and photocatalytic property of the material. An analysis of the results showed an ...

One-dimensional rutile TiO2 nanorod arrays with a tunable morphology and intact crystalline sub-nano structures attached are successfully fabricated as a large-scale film based on substrates. An anatase/rutile TiO2 crystal structure grown in a hierarchical architecture is achieved by forming hybrid organic–inorganic interfaces in a solvent-based environment. The oriented attachment growth dominant pathway provides an easy and reproducible method to synthesize unnaturally shaped nanostructures with heterogeneous crystalline structures, the co-existence of which is difficult in one-dimensional array systems. The morphology and crystal structures of the attached sub-nano nanoparticles are also highly related to the solvent composition ratio due to the hydrolysis–condensation reaction. The small misorientation between the lattice planes of the two distinct phases leads to the formation of interface dislocations, which are assigned as oriented attachment growth-induced defects. Resonant inelastic X-ray scattering reveals that the obvious dd excitation feature of the TiO2 nanorod arrays after the sub-nano structure attachment is related to the growth-induced oxygen vacancies, which demonstrates the existence of Ti3+ at the interface. The interface Ti3+ can activate the Ti–OH species, resulting in an enhancement in photocatalytic activity. TiO2 nanorod arrays based on substrates with heterogeneous crystal structures and remarkable crystalline stability have potential as promising photocatalysts in the energy and environmental fields.

Designing highly efficient oxygen evolution reaction (OER) electrocatalysts is very important for various electrochemical devices. In this work, for the first time, we have successfully generated coordinatively unsaturated metal sites (CUMSs) in phytic acid–Co2+ (Phy–Co2+) based metal–organic complexes by engineering the coordination geometry with room-temperature plasma technology. The CUMSs can serve as active centers to catalyze the OER. The electron spin resonance and X-ray absorption spectra provide direct evidence that the coordination geometry is obviously modified with many CUMSs by the plasma treatment. The plasma treated Phy–Co2+ (P-Phy–Co2+) only requires an overpotential of 306 mV to reach 10 mA cm−2 on glassy carbon electrodes. When we expand this strategy to a CoFe bimetallic system, it only needs an overpotential of 265 mV to achieve 10 mA cm−2 with a small Tafel slope of 36.51 mV dec−1. P-Phy–Co2+ is superior to the state-of-the-art. Our findings not only provide alternative excellent OER electrocatalysts, but also introduce a promising principle to design advanced electrocatalysts by creating more CUMSs.

The electrodeposition nature of copper on a gold electrode in a 4.8 pH CuSO4 solution was inquired using X-ray absorption spectroscopy, electrochemical quartz crystal microbalance, and thermal desorption spectroscopy techniques. Our results point out that the electrodeposition of copper prompts the formation of stable oxi-hydroxide species with a formal oxidation state Cu+ without the evidence of metallic copper formation (Cu0). Moreover, the subsequent anodic polarization of Cu2Oaq yields the formation of CuO, in the formal oxidation state Cu2+, which is dissolved at higher anodic potential. It was found that the dissolution process needs less charge than that required for the electrodeposition indicating a nonreversible process most likely due to concomitant water splitting and formation of protons during the electrodeposition.

We study the implications of FeCo underlayer and overlayer on the static and dynamic magnetic properties of FeCo/FePt exchange spring system along with post-annealing kinetics. Probing of FePt/FeCo/Si and FeCo/FePt/Si bilayers using high energy synchrotron X-ray diffraction by varying glancing angles unveiled structural variations at the interface, where FeCo is observed to inhibit the crystalline growth of FePt. A soft ferromagnetic in-plane behavior and defect-driven hard ferromagnetic properties in the out-plane configuration are established. Besides, the magnetization dynamics studied by Ferromagnetic Resonance depicts an out-plane magnetization component of FePt only in FeCo/FePt/Si. X-ray Absorption Spectroscopy (XAS) in the Fe, Co and Pt L-edge regions reveal dissimilar interfaces in the two series due to thermal agitation effects. XAS spectra at Fe and Co K-edges ensure similar local coordination of Co immaterial of stack order, contrary to altered local geometry of Fe observed in the two series ascribed to varied crystallinity of FePt. Such structures are useful for spin-wave assisted low field magnetization switching in highly coercive FePt by using exchange coupled soft FeCo.

Integrating a bioelectrochemical system with CO2 electroreduction (CO2ER) can achieve recovery of resources and conversion of value-added chemicals, but it still faces challenge of high overpotential and poor selectivity. Herein, we report a CO2ER catalyst with iron bonded to nitrogen atoms (Fe-Nx) anchored hierarchical porous carbon (Fe SA-NC) by a molecular-confined pyrolysis strategy. Owing to the high surface area and atomic-level Fe-N4 sites, Fe SA-NC possessed superior CO2-to-CO conversion performance with a low overpotential of 90 mV, a small Tafel slope of 92 mV dec−1, and high Faradaic efficiency of 95.9% at −0.5 V, superior to almost all previously reported Fe-Nx based carbon materials for CO2ER. Experimental results manifested the atomic-level Fe-N4 sites in carbon frameworks with a single Fe atom coordinating four N atoms. Theoretical calculations revealed Fe-N4 sites weaken the free energy for the formation of *COOH intermediate, and the short Fe-C bond length in the structure of *COOH absorbed on Fe-N4 sites accelerated the electron transfer from Fe-N4 centers to *COOH, thus boosting the reaction kinetics. An integrated device with cathodic Fe SA-NC and bioanode can recover energy and carbon resource from wastewater, delivering maximum current and CO production rate of 1.54 ± 0.05 mA and 33.66 ± 0.58 mmol g−1cat h−1.

This study investigated the ultrathin Cu(002) capping nano-island effects on the magnetic characterizations and microstructure of epitaxial FePt(001) films directly fabricated on MgO(001) substrates at the relatively low temperature of 300 °C via electron-beam deposition. The enhancement of the coercivity is attributed to the lowered exchange coupling of FePt magnetic grains that begun from Cu atom behavior of spreading in many directions mainly along grain boundaries due to its lower surface energy than that of pure Fe or Pt. The measurement of angular-dependent coercivity shows a tendency of a domain-wall motion shift toward the rotation of the reverse-domain type upon the thickness of the Cu capping nano-island layer atop the FePt films. The intergranular interaction was clarified by the Kelly–Henkel plot, which indicated that there was strong exchange coupling (positive δM) between neighboring grains in the FePt continuous films without Cu capping nano-islands. On the other hand, a negative δM value was gained when the FePt films were capped with a Cu(002) single layer, indicating that the Cu capping layer can be used to control the strength of intergrain exchange coupling between the adjacent FePt grains and thicker Cu(002) capping nano-islands toward magnetic isolation, thus, there was an existence of dipole interaction in our designed Cu/FePt composite structure of stacked films.

Inspired by photosynthesis in nature, artificial photosynthesis (AP) systems have been widely investigated in the context of energy and environmental research. Here we report a noble-metal-free AP system for visible-light-driven H2 generation from aqueous solutions consisting of fluorescein (FL) as photosensitizer, single-layer ultrasmall MoS2 nanoplates embedded in carbon nanofibers (CNF) as electron relay and redox catalyst, and triethanolamine (TEOA) as sacrificial electron donor. This CNF–MoS 2/FL system exhibits outstanding H2 evolution performance, with an H2 generation rate that exceeds not only both MoS2/FL (by 100%) and CNF/FL (by 1100%), but also the Pt/FL system (by 40%). The excellent photocatalytic activity of this CNF–MoS2/FL system can be ascribed to the synergistic effects of CNF and MoS2 coupling: (1) the simultaneous presence of MoS2 with its delocalized and increased Mo 4d unoccupied states and of CNF with increased graphitic characteristics enables electron transfer from FL∗ to MoS2 via CNF electron relay; (2) the single-layered ultrasmall MoS2 nanoplates with short effective lengths for electron transfer and high density of reactive S-edges effectively catalyze the H2 evolution reaction (HER). The presented work successfully fabricated a highly efficient AP system for solar H2 production from a fully aqueous solution and indicated CNF–MoS2 as a promising candidate to replace Pt for solar fuel conversion.

The effects of growth time and interface between the iron oxyhydroxide (FeOOH) and carbon materials (carbon nanotubes (CNT) and reduced graphene oxide (RGO)) to form an asymmetric supercapacitor was studied by X-ray absorption spectroscopy (XAS) and electrochemical measurements. FeOOH/CNT (FCNT) and FeOOH/RGO (FRGO) were successfully synthesized by a simple spontaneous redox reaction with FeCl3. The RGO functions as an ideal substrate, providing rich growth sites for FeOOH, and it is believed to facilitate the transport of electrons/ions across the electrode/electrolyte interface. FRGO has been identified as a supercapacitor and found to exhibit significantly greater capacitance than FCNT. To gain further insight into the effects of growth times and the interface of FeOOH for FCNT and FRGO, the electronic structures of FCNT and FRGO with various FeOOH growth times were elucidated by XAS. The difference between the surface electronic structures of CNT and RGO yields different nucleation and growth rates of...

Owing to the current energy crisis and extreme changes in the global climate, there is great interest in finding renewable energy resources. Vast progress has been made in the development of new materials related to renewable energy, and their physical/chemical properties can be tailored by nanostructuring and other advanced synthetic approaches. In many important energy systems, such as solar hydrogen systems, the atomic/electronic structures of materials and fundamental interfacial phenomena of systems critically determine the energy conversion efficiency of materials [1, 2]. Without knowledge of the fundamental electronic structures of the materials during conversion reactions, better engineering of the material for practical use is difficult. Understanding and controlling the interfaces in energy generation/conversion/storage materials requires in-situ/operando approaches [3, 4]. The Taiwan Photon Source (TPS) Soft X-ray Spectroscopic beamline provides the capabilities for X-ray absorption (XAS) and X...

Silicon is a promising photocathode material for solar hydrogen evolution because of its small band gap, negative conduction band position, and ideal theoretical current density. In this study, p-type Si microwire ( p -Si MW) arrays were prepared as photocathodes because of the large surface area and high light-harvesting capability. However, Si MWs suffered from low photocatalytic activity because of slow photo-induced carriers during driving of water-splitting reaction. Therefore, molybdenum sulfide (MoS 2 ) with appropriate band alignment with p-Si material was employed for surface modification to function as a co-catalyst for collecting photo-generated minority carriers and reducing recombination possibility. The onset potential and current density at 0 V versus reversible hydrogen electrode (RHE) of Si@MoS 2 MWs were +0.122 V and −8.41 mA cm −2 . Heterometal atoms were employed to dope MoS 2 co-catalyst and expose more sulfur-terminated active sites to further boost photoelectrochemical performance. Optimal activity of Si@MMoS x (M = Fe, Co, Ni) was achieved by doping Co heteroatoms, and its turn-on voltage and photocurrent density at 0 V (vs. RHE) were respectively increased to +0.192 V and −17.2 mA cm −2 . X-ray absorption spectroscopy was applied to demonstrate that Fe ions of FeMoS x were dichalcogenide materials, forming a composite with MoS 2 and contributing better photoelectrolytic efficiency. By contrast, two-valent heteroatoms of CoMoS x and NiMoS x substituted the Mo 4+ ions in MoS 2 . For charge compensation, more defects and edges were revealed as active sites of solar hydrogen production by adding Co or Ni dopants in MoS 2 co-catalyst, which led to lower overpotential.

It is of essential importance to design an electrocatalyst with excellent performance for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in water splitting. Co3O4 has been developed as a highly efficient OER electrocatalyst, but it has almost no activity for HER. In a previous study, it has been demonstrated that the formation of oxygen vacancies (VO) in Co3O4 can significantly enhance the OER activity. However, the stability of VO needs to be considered, especially under the highly oxidizing conditions of the OER process. It is a big challenge to stabilize the VO in Co3O4 while reserving the excellent activity. Filling the oxygen vacancies with heteroatoms in the VO-rich Co3O4 may be a smart strategy to stabilize the VO by compensating the coordination numbers and obtain an even surprising activity due to the modification of electronic properties by heteroatoms. Herein, we successfully transformed VO-rich Co3O4 into an HER-OER electrocatalyst by filling the in situ formed VO in Co3O4 with phosphorus (P-Co3O4) by treating Co3O4 with Ar plasma in the presence of a P precursor. The relatively lower coordination numbers in VO-Co3O4 than those in pristine Co3O4 were evidenced by X-ray adsorption spectroscopy, indicating that the oxygen vacancies were created after Ar plasma etching. On the other hand, the relatively higher coordination numbers in P-Co3O4 than those in VO-Co3O4 and nearly same coordination number as that in pristine Co3O4 strongly suggest the efficient filling of P in the vacancies by treatment with Ar plasma in the presence of a P precursor. The Co–O bonds in Co3O4 consist of octahedral Co3+(Oh)–O and tetrahedral Co2+(Td)–O (Oh, octahedral coordination by six oxygen atoms and Td, tetrahedral coordination by four oxygen atoms). More Co3+(Oh)–O are broken when oxygen vacancies are formed in VO-Co3O4, and more electrons enter the octahedral Co 3d orbital than those entering the tetrahedral Co 3d orbital. Then, with the filling of P in the vacancy site, electrons are transferred out of the Co 3d states, and more Co2+(Td) than Co3+(Oh) are left in P-Co3O4. These results suggest that the favored catalytic ability of P-Co3O4 is dominated by the Co2+(Td) site. P-Co3O4 shows superior electrocatalytic activities for HER and OER (among the best non-precious metal catalysts). Owing to its superior efficiency, P-Co3O4 can directly catalyze overall water splitting with excellent performance. The theoretical calculations illustrated that the improved electrical conductivity and intermediate binding by P-filling contributed significantly to the enhanced HER and OER activity of Co3O4.

Skutterudites are emerging as potential candidates that show high efficiency and thus provide an ideal platform for research. The properties of nanostructured films of skutterudites are different from those of the corresponding bulk. The present study reports the evolution of nanostructured single-phase CoSb3 fabricated by using low-energy ion irradiation of Co/Sb bilayer films and subsequent annealing at an optimized temperature and their Seebeck coefficients (S). The effects of ion beam parameters with annealing on the phase evolution and nanostructure modifications were studied. An increase in Xe+ ion fluence resulted in complete mixing of Co/Sb on postannealing forming flower-like nanostructures of single phase CoSb3. The temperature-dependent electrical resistivity (ρ) increases with the ion fluence because of defect creation which further increases on postannealing due to surface nanostructuring. The S of these films of CoSb3 is found to be higher and this is attributed to the formation of a uniform layer of nanostructured CoSb3 alloy thin film. The S and Hall coefficients of all these films are negative implying that they are n-type semiconductors.

Electrocatalytic water splitting is a key technique to produce hydrogen fuels, which can be considered as an efficient strategy to store renewable energy. Oxygen evolution reaction (OER) that occurs at the anode side requires a four-electron transfer under highly oxidizing conditions. OER has a large overpotential and therefore determines the overall efficiency. Certain electrocatalysts can efficiently help to improve the reaction kinetics. Owing to the high cost of precious metals such as Pt, Ru, and Ir, non-precious metal oxide catalysts have been vigorously investigated under alkaline conditions. Herein, we synthesized novel highly dispersed amorphous CoOxfor the first time in the form of a cluster favorable to enhance the OER activity using a facile method via the air dielectric barrier discharge (DBD) plasma. Compared with the pristine biopolymer–cobalt complex, the amorphous CoOx cluster exhibits a much higher current density and a lower overpotential for OER, e.g., the overpotential of 290 mV at 10 mA cm−2 and the overpotential of only 350 mV at 300 mA cm−1. The excellent electrocatalytic OER activity was attributed to the unsaturated catalytic sites on the amorphous CoOx cluster. In addition, we studied the reaction mechanism, and it was observed that pure O2 DBD plasma could lead to the evolution of crystalline CoOx; however, the presence of N2 and O2 in DBD plasma could ensure the facile evolution of amorphous CoOx clusters. This study provides a new strategy to design amorphous materials for electrocatalysis and beyond.

In anode, electrocatalytic water splitting involves oxygen evolution reaction (OER), which is a complex and sluggish reaction, and thus the efficiency to produce hydrogen is seriously limited by OER. We report that CoTe2 exhibits optimized OER activity for the first time. Multiwalled carbon nanotube (MWCNT) is utilized to support CoTe2 in generating a synergistic effect to enhance OER activity and improve stability by tuning different loading amounts of CoTe2 on CNT. In 1.0 M KOH, bare CoTe2 needed overpotential of 323 mV to produce 10 mA/cm2 with Tafel slope of 85.1 mV/dec, but CoTe2/carbon nanotube (CNT) with optimized loading amount of CoTe2 required only 291 mV to produce10 mA/cm2 with Tafel slope of 44.2 mV/dec. X-ray absorption near edge structure (XANES) was applied to prove that an electron transfer from eg band of CoTe2 to CNT caused a synergistic effect. This electron transfer modulated the bond strength of oxygen-related intermediate species on the surface of catalyst and optimized OER performa...

Cobalt oxides as efficient oxygen evolution reaction (OER) electrocatalysts have received much attention because of their rich reserves and cheap cost. There are two common cobalt oxides, Co3 O4 (spinel phase, stable but poor intrinsic activity) and CoO (rocksalt phase, active but easily be oxidatized). Constructing Co3 O4 /CoO heterophase can inherit both characteristic features of each component and form a heterophase interface facilitating charge transfer, which is believed to be an effective strategy in designing excellent electrocatalysts. Herein, an atomic arrangement engineering strategy is applied to improve electrocatalytic activity of Co3 O4 for the OER. With the presence of oxygen vacancies, cobalt atoms at tetrahedral sites in Co3 O4 can more easily diffuse into interstitial octahedral sites to form CoO phase structure as revealed by periodic density functional theory computations. The Co3 O4 /CoO spinel/rocksalt heterophase can be in situ fabricated at the atomic scale in plane. The overpotential to reach 10 mA cm-2 of Co3 O4 /CoO is 1.532 V, which is 92 mV smaller than that of Co3 O4 . Theoretical calculations confirm that the excellent electrochemical activity is corresponding to a decline in average p-state energy of adsorbed-O on the Co3 O4 /CoO heterophase interface. The reaction Gibbs energy barrier has been significantly decreased with the construction of the heterophase interface.

Facile and reliable screening of cost-effective, high-performance and scalable electrocatalysts is key for energy conversion technologies such as water splitting. ABO3-δ perovskites, with rich constitutions and structures, have never been designed via activity descriptors for critical hydrogen evolution reaction (HER). Here, we apply coordination rationales to introduce A-site ionic electronegativity (AIE) as an efficient unifying descriptor to predict the HER activities of 13 cobalt-based perovskites. Compared with A-site structural or thermodynamic parameter, AIE endows the HER activity with the best volcano trend. (Gd0.5La0.5)BaCo2O5.5+δ predicted from an AIE value of ~2.33 exceeds the state-of-the-art Pt/C catalyst in electrode activity and stability. X-ray absorption and computational studies reveal that the peak HER activities at a moderate AIE value of ~2.33 can be associated with the optimal electronic states of active B-sites via inductive effect in perovskite structure (~200 nm depth), including Co valence, Co-O bond covalency, band gap and O 2p-band position., Facile and reliable screening of efficient electrocatalysts is important for energy conversion technologies such as water splitting. Here, authors introduce A-site ionic electronegativity as a descriptor to understand the hydrogen-evolution activities of cobalt-based perovskites.

Electronic structure greatly determines the band structures and the charge carrier transport properties of semiconducting photocatalysts and consequently their photocatalytic activities. Here, by simply calcining the mixture of graphitic carbon nitride (g-C3 N4 ) and sodium borohydride in an inert atmosphere, boron dopants and nitrogen defects are simultaneously introduced into g-C3 N4 . The resultant boron-doped and nitrogen-deficient g-C3 N4 exhibits excellent activity for photocatalytic oxygen evolution, with highest oxygen evolution rate reaching 561.2 µmol h-1 g-1 , much higher than previously reported g-C3 N4 . It is well evidenced that with conduction and valence band positions substantially and continuously tuned by the simultaneous introduction of boron dopants and nitrogen defects into g-C3 N4 , the band structures are exceptionally modulated for both effective optical absorption in visible light and much increased driving force for water oxidation. Moreover, the engineered electronic structure creates abundant unsaturated sites and induces strong interlayer C-N interaction, leading to efficient electron excitation and accelerated charge transport. In the present work, a facile approach is successfully demonstrated to engineer the electronic structures and the band structures of g-C3 N4 with simultaneous introduction of dopants and defects for high-performance photocatalytic oxygen evolution, which can provide informative principles for the design of efficient photocatalysis systems for solar energy conversion.