Resultados de investigación

20 pages. -- Experimental: Raw Materials. -- Modifications and Syntheses of Materials. -- Characterization techniques. -- Operando XRD Characterization. -- Batteries. -- Finite element simulations. Figures S1-S13 . -- Table S2. Interlayer distance (0 0 2) statistics of Gr and SC. -- Table S3. Definition of parameters of matrix polynomial for GrS electrode.. -- Table S4. Definition of parameters of matrix polynomial for SCS electrode., Peer reviewed

Figures S1-S9. -- Spreadsheet S1-S5., 1-s2.0-S0008622323005870-mmc1.docx, 1-s2.0-S0008622323005870-mmc2.xlxs, Peer reviewed

13 pages. -- S1: Determination of areas and formation of metallic iridium and derived iridium oxide. -- S2: Electrodeposition of Co and Ni in deep eutectic solvents. -- S3: Influence of time and temperature on the GDR of Co and Ni by Ir(IV). -- S4: Energy dispersive X-ray Spectroscopy (EDX) analysis. -- S5: Precipitating IrOx. -- S6. Influence on the OER by the gold substrates. -- S7: Surface area activity at the oxygen evolution reaction., Complementary CVs, CAs, FE-SEM images and EDX analysis of the prepared IrO2 films after GDR are provided., Peer reviewed

Source data for manuscript "Real-time microscopy of the relaxation of a glass" (DOI: 10.1038/s41567-023-02125-0), including: AFM source images and data points for all plots in the manuscript., AFM images Figures 1, 3, 4.rar, Figure 1c profile centre.txt, Figure 1c profile left.txt, Figure 1c profile right.txt, Figure 1d.txt, Figure 2c AFM.txt, Figure 2c FEM.txt, Figure 3a inset.txt, Figure 3a.txt, Figure 4a Growth1.txt, Figure 4a Growth2.txt, Figure 4a Growth3.txt, Figure 4a Growth4.txt, Figure 4a Growth5.txt, Figure 4a Growth6.txt, Figure 4a Growth7.txt, Figure 4b.txt, Peer reviewed

11 pages. -- Experimental Section. Chemicals. -- Synthesis of Hexaaminobenzene (HAB). -- Synthesis of C2N. --Synthesis of PdH0.58@C2N, Pd@C2N, PdH0.58 and PdH0.58/C2N. -- -- Structural characterization. -- Electrochemical Measurements. -- Computational method. -- Figures S1-S8. -- Table S1. Summary of the FOR activity and stability of Pd-based nanoalloys., The lack of electrocatalysts for the formate oxidation reaction (FOR) hampers the deployment of direct formate fuel cells (DFFCs). To overcome this limitation, herein, we detail the production of palladium hydride particles supported on C2N (PdH0.58@C2N) via a facile method. PdH0.58@C2N displays excellent FOR performance, reaching current densities up to 5.6 A·mgPd–1 and stable cycling and chronoamperometric operation. The Pd lattice expands due to the hydrogen intercalation. Besides, an electronic redistribution associated with the distinct electronegativity of Pd and H is observed. Both phenomena modify the electron energy levels, enhancing the activity and stability of the composite catalyst. More specifically, differential functional theory calculations show H intercalation to downshift the Pd d-band center in Pd0.58@C2N, weakening adsorbate binding and accelerating the FOR rate-determining step., Peer reviewed

Under a Creative Commons license CC BY 4.0 deed., Figure S1. Molecular structure of SY, SEM and AFM micrographs of the ZTO layer. Figure S2. HRTEM micrograph and SAED pattern of S-ZnO NWs. Figure S3. TEM micrographs of ZnO nanowires. Figure S4. Gate leakage current in control, S-NWs, and L-NWs LEEFTs. Figure S5. Output characteristics of control, S-NWs, and L-NWs LEEFTs. Figure S6. Variable channel HLET image. Figure S7. Transmittance from the top MoOx/Ag electrodes. Figure S8. AFM images of NWs. Figure S9. 3D reconstruction of AFM images in GPVDM. Figure S10. Ray tracing simulation example 300-700nm. Figure S11. Calculation efficiency as a function of layer height of the L-NWs layer. Table S1. Comparison with literature, M.U.C., A.G.-G., and R.J.B. thank the Northern Accelerator for feasibility funding Grant # NACCF231 and Durham University for Grant Seedcorn Funds WT#801498. M.U.C. further thank EPSRC (New Investigator Award # EP/V037862/1 and Capital Equipment Grant EC/RF080422) for financial support., Peer reviewed

Electrochemical characterization: Figure S3 shows the linear sweep voltammetries of the different catalysts subjected to several cycles of acid leaching/thermal treatments. Catalysts were named as Fe-N-CXG-X-Tn, where X represents the activation method (CO2, H2O and KOH) and Tn indicates the number of cycles of acid leaching/thermal treatment performed over each catalyst. The curve with the highest activity is plotted with a thicker line, to highlight the number of cycles giving rise to the most active catalyst.-- Under a Creative Commons license BY 4.0., Reaction for carbon activation with CO2: S1. Reactions for carbon activation with water vapour: S2, S3, S4, S5. Reactions that can take place during carbon activation with KOH [1]: S6, S7, S8, S9, S10, S11, S12, S13, S14. Physicochemical characterization: Figure S1 XPS high resolution O1s spectra for (a) CXG, (b) CXG-CO2 (c) CXG-H2O and (d) CXG-KOH considering 30 % Gaussian and 70% Lorentzian peak shape and Shirley background; Figure S2: XPS high resolution C1s spectra for (a) CXG, (b) CXG-CO2 (c) CXG-H2O and (d) CXG-KOH considering 30 % Gaussian and 70% Lorentzian peak shape and Shirley background; Table S1: Chemical composition determined by ICP, elemental analysis and XPS for Fe-N-CXG catalysts; Electrochemical characterization: Figure S3 Polarization curves for the ORR, in RDE at 1600 rpm in O2-saturated 0.5M H2SO4 for a) Fe-N-CXG, b) Fe-N-CXG-CO2, c) Fe-N-CXG-H2O, d) Fe-N-CXG-KOH subjected to successive cycles of acid leaching/thermal treatments indicated as Tn (n is the number of cycles performed). Figure S4 Polarization curve and power density curve for commercial Pt/C catalyst at the cathode and anode (0.2 mgPt cm-2), Nafion® NR212 membrane. Operating conditions: 80 °C; H2/O2 at λ= 1.3/1.5, 100% RH, and back pressure of 1.5 bar-gauge. Figure S5: Detail pictures of a drop of water on the surface of electrodes. a) Fe-NCXG, b) Fe-N-CXG-CO2, c) Fe-N-CXG-H2O, d) Fe-N-CXG-KOH. Figure S6. (a) Polarization curves and (b) power density curves after at the end of test (EoT), consisting of 20h operation at 0.5 V. Fe-N-CXG catalysts (4 mg cm-2) at the cathode, Nafion® NR212 membrane, and Pt40%/C (0.2 mgPt cm-2) at the anode. Operating conditions: 80 °C; H2/O2 at λ= 1.3/1.5, 100% RH, and back pressure of 1.5 bar-gauge., The authors wish to acknowledge the grant PID2020-115848RB-C21 funded by MCIN/AEI/10.13039/501100011033. This research has received funding from the European Institute of Innovation and Technology (EIT) through project EIT RM – n. 18252. Authors also acknowledge Gobierno de Aragón (DGA) for the financial support to Grupo de Conversión de Combustibles (T06_23R). L. Álvarez acknowledges also DGA for her pre-doctoral contract., Peer reviewed

12 pages. -- Figures S1-S15. -- Table S1. The atomic parameters obtained from Rietveld refinement result. -- Table S2. The Li+ diffusion coefficients (DLi+(×10-10cm2s-1) derived from the GITT measurements during the 10th and 50th charge/discharge., Doping could effectively tune the electrochemical performance of layered oxide cathodes in Li-ion batteries, whereas the working mechanism is usually oversimplified (i.e., a “pillar” effect). Although the Jahn–Teller effect is generally regarded as the fundamental origin of structural instability in some oxides, more polyhedral distortions are associated with pseudo-JTE (PJTE), which involves vibronic couplings. In this work, the atomic structures of doped LiCoO2 by Mg cations, F anions, and both were investigated thoroughly to reveal the atomic environments of these dopants and their influence on electrochemical performance. The function of these dopants as pillars is well discussed from the view of PJTE manipulation. Briefly, the MgO4 tetrahedra in Mg-doped LiCoO2 could suppress the charge transfer from the ligand to Co in neighboring octahedra, thus depressing PJTE. Although F doping does increase the ligand-field strength, the induced octahedral distortion reduces the structural stability dramatically. Comparatively, Mg/F co-doping generates the CoO5F–MgO4F2–CoO5F medium-range orders (MROs), which could depress both structural distortion and charge transfer in Co-centered octahedra for reduced PJTE. The reduced PJTE accounts for the improved electrochemical performance, making the co-doped LiCoO2 offer the best performance: a 70% capacity retention after 200 cycles within the potential range of 2.8–4.6 V, followed by Mg-doped LiCoO2. In contrast, although F-doping could induce an extra rock salt-like surface layer for higher capacity, its cycling improvement is rather limited. These results highlight the importance of structural modulation in enhancing the material performance and propose that the manipulation of PJTE would be an effective strategy in developing novel high-performance oxide cathodes., Peer reviewed

20 pages. -- S1. X-Ray Diffraction Structural Data. -- S2. Additional STM images and LEED. -- S3. XPS analysis. -- S4. XNLD additional results. -- S5. Ligand Field Multiplet simulations. -- S6. XMCD(H) of {Cr10}/Au samples. -- S7. Monte Carlo calculations. -- S8. Cluster anisotropy calculation. -- S9. Mean field exchange coupling constant, Peer reviewed

26 pages. -- Fig. S1. XRD pattern of Cu(OH)2 collected from the sonication of the Cu(OH)2@CuM electrode. -- Fig. S2. XRD pattern of Ni(OH)2/Cu(OH)2 collected from the sonication of the Ni(OH)2/Cu(OH)2@CuM electrode. -- Fig. S3. XRD pattern of NiO/CuO collected from the sonication of the NiO/CuO@CuM electrode. -- Fig.S4. The diffraction spots pattern analysis of Fig 2c. -- Fig. S5. HRTEM images and corresponding indexed FFT of a NiO/CuO nanostructure. -- Fig. S6. HRTEM images and corresponding indexed FFT of a NiO/CuO nanostructure. -- Fig. S7. (a) SEM image of CuO@CuM. The inset shows an optical image of a self-supported electrode. (b) XRD pattern of CuO collected from the sonication of the CuO@CuM electrode. -- Fig. S8. HAADF STEM image and EELS elemental maps of Cu and O of CuO nanostructures. -- Fig. S9. SEM image of Ni(OH)2 directly grown on a copper mesh. The inset shows an optical image of the electrode. -- Fig. S10. SEM image of Ni(OH)2 directly grown on a CuM with the hydrothermal method. The inset shows an optical image of the electrode. (a) Hydrothermal method with the precursor of 1 mmol nickel nitrate, 2 mmol NaOH, 20 ml ethylene glycol and 4 ml H2O, as well as one piece of the cleaned CuM at 100 C for 300 min. (b) Hydrothermal method with the precursor of 1 mmol nickel acetylacetonate, 2 mmol urea, 1 mL butylamine, 20 ml ethylene glycol and 4 ml H2O as well as one piece of the cleaned CuM at 200 C for 180 min. -- Fig. S11. Survey XPS spectra of CuO@CuM and NiO/CuO@CuM. -- Fig. S12. Current density vs. urea concentration of NiO/CuO@CuM electrode at different specific applied potential. -- Fig. S13. LSV curves of NiO/CuO@CuM with the active process. -- Fig. S14. CV curves of (a) NiO/CuO@CuM, (b) Ni(OH)2/Cu(OH)2@CuM, (c) CuO@CuM, and (d) Cu(OH)2@CuM with different scan rates. -- Fig. S15. ECSA values of NiO/CuO@CuM, Ni(OH)2/Cu(OH)2@CuM, CuO@CuM, and Cu(OH)2@CuM electrode. -- Fig. S16. LSV curves of NiO/CuO@CuM electrode before and after stability measurements. -- Fig. S17. SEM image of NiO/CuO@CuM after stability measurements. -- Fig. S18. XRD pattern of NiO/CuO structure before and after stability tests. -- Fig. S19. (a) Cu 2p and (b) Ni 2p high-resolution XPS spectra of self-supported NiO/CuO@CuM electrodes after stability tests. -- Fig. S20. Raman spectra of NiO/CuO@CuM p-p heterojunction electrode (a) before and (b) after UOR stability test. -- Fig. 21. (a) SEM image of Ni(OH)2/CuO@CuM. (b) XRD pattern of Ni(OH)2/CuO nanostructure. (c) LSV curves (d) Tafel slopes of different electrodes in 1.0 M KOH with 0.5 M urea. (e) CV curves of Ni(OH)2/CuO@CuM electrode. (f) Cdl values of different electrodes. -- Fig. S22. (a) Top-view and (b) side-view of optimized structures of NiOOH/CuO heterojunction. -- Fig. S23. (a) Top-view and (b) side-view of optimized structures of NiOOH. (c) Top-view and (d) side-view of optimized structures of CuO. -- Fig. S24. PDOS and d band center of (a) pristine CuO, (b) NiOOH and (c) CuO/NiOOH heterojunctions with DFT+U (up) and DFT+U-D3 methods (down), respectively. -- Fig. S25. The slices of electron density difference of urea adsorbed on (a) pristine CuO, and (b) NiOOH. The contour around the atoms represents electron accumulation (red) or electron depletion (blue). The balls with various colors mean different atoms: red-O, gray-C, white-H, orange-Cu, dark blue-N, and watery blue-Ni. -- Fig. S26. (a) Bond length (Å) of urea molecule adsorbed on the NiOOH/CuO heterojunction surface. (b) Bond length (Å) of free urea molecule. -- Fig. S27. Slices of electron density difference of CO2 adsorbed on (a) pristine CuO, (b) NiOOH, and (c) NiOOH/CuO heterojunction. The contour around the atoms represents electron accumulation (red) or electron depletion (blue). The balls with various colors mean different atoms: red-O, gray-C, white-H, orange-Cu, and watery blue-Ni. -- Fig. S28. (a) The structure of DUFCs with an ion exchange membrane (IEM), (b) voltage-current and power-current curves of DUFCs with different self-supported anodes electrodes, (c) the open circuit voltage and (d) power density of DUFCs with different self-supported anodes electrodes. -- Table S1. The analysis results of the diffraction spots pattern of Fig. 2c. -- Table S2. Elements ratio of NiO/CuO@CuM and CuO@CuM by EDS and XPS techniques. -- Table S3. EIS fitting results of NiO/CuO@CuM, Ni(OH)2/Cu(OH)2@CuM, CuO@CuM and Cu(OH)2/@CuM. -- Table S4. Comparison of electrochemical UOR performance of this work with other reported electrodes. NF = nickel foam; GC = glassy carbon, CP = carbon paper, CC = carbon cloth. -- Table S5. Bond lengths of Cu-O and Ni-O at the bulk and heterojunction interface. -- Table S6. Comparison of DUFC performance with NiO/CuO@CuM as the anode and previously reported electrocatalysts., Peer reviewed