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A potential application of two-dimensional (2D) MXenes, such as Ti2CTx and Ti3C2Tx, is energy storage devices, such as supercapacitors, batteries, and hydride electrochemical cells, where intercalation of ions between the 2D layers is considered as a charge carrier. Electrochemical cycling investigations in combination with Ti 1s x-ray absorption spectroscopy have therefore been performed with the objective to study oxidation state changes during potential variations. In some of these studies Ti3C2Tx has shown main edge shifts in the Ti 1s x-ray absorption near-edge structure. Here we show that these main edge shifts originate from the Ti 4p orbital involvement in the bonding between the surface Ti and the termination species at the fcc-sites. The study further shows that the t2g–eg crystal field splitting (10Dq) observed in the pre-edge absorption region indicate weaker Ti–C bonds in Ti2CTx and Ti3C2Tx compared to TiC and the corresponding MAX phases. The results from this study provide information necessary for improved electronic modeling and subsequently a better description of the materials properties of the MXenes. In general, potential applications, where surface interactions with intercalation elements are important processes, will benefit from the new knowledge presented., Funding agencies: the Swedish Research council under contract 2018-07152, the Swedish Governmental Agencyfor Innovation Systems under Contract 2018-04969,and Formas under Contract 2019-02496. We also thank the Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-MatLiU No. 2009 00971). M M acknowledges financial support from the Swedish Energy Research (Grant No. 43606-1) and the Carl Tryggers Foundation (CTS20:272, CTS16:303, CTS14:310). The FEFF calculations of scattering paths were performed using supercomputer resources provided by the National Academic Infrastructure for Supercomputing in Sweden (NAISS) at Linköping University funded by the Swedish Research Council through GrantAgreement No. 2022-06725

Structural changes in Ti1-xAlxN coated tool inserts used for turning in 316L stainless steel were investigated by XANES, EXAFS, EDS, and STEM. For coarse-grained fcc-structured Ti1-xAlxN coatings, with 0 ≤ x ≤ 0.62, the XANES spectrum changes with Al-content. XANES Ti 1s line-scans across the rake face of the worn samples reveals that TiN-enriched domains have formed during turning in Ti0.47Al0.53N and Ti0.38Al0.62N samples as a result of spinodal decomposition. The XANES spectra reveal the locations on the tool in which the most TiN-rich domains have formed, indicating which part of the tool-chip contact area that experienced the highest temperature during turning. Changes in the pre-edge features in the XANES spectra reveal that structural changes occur also in the w-TiAlN phase in fine-grained Ti0.38Al0.62N during turning. EDS shows that Cr and Fe from the steel adhere to the tool rake face during machining. Cr 1s and Fe 1s XANES show that Cr is oxidized in the end of the contact length while the adhered Fe retains in the same fcc-structure as that of the 316L stainless steel., Funding agencies: Swedish Governmental Agency for Innovation Systems (Vinnova) [2018-04417]; VINNOVA [2016-05156]; Swedish Research council [2018-07152]; Swedish Governmental Agency for Innovation Systems [2018-04969]; Formas [2019-02496]

MXenes are an interesting family of 2D materials that have the potential to meet challenges in many applications. A useful tool in the work of understanding the nature of the MXenes, as well as exploring their capabilities, is Xray photoelectron spectroscopy (XPS). In analyzing XPS spectra it might be necessary to use curve fitting to extract valuable information. However, approaches toward the curve fitting procedure have been different in many studies and introductions of questionable assumptions, unverified feature assignments, and inconsistent curve fitting have led to contrasting conclusions from XPS analysis. It is therefore motivated to show curve fittings of F 1s, O 1s, Ti 2p, and C 1s XPS spectra obtained from high quality Ti3C2Tx that are based on fundamental knowledge applied step by step through the strategy of first principles thinking. With the use of first principles thinking the curve fittings and the subsequent analysis became more realistic compared to what have been presented in recent studies. The results of the curve fittings presented in this work are well founded and can be used as a model for future curve fittings of MXenes. The strategy of first principles thinking is advantageous in XPS curve fittings in general., Funding Agencies|Swedish Foundation for Strategic Research (SSF) [EM16-0004]; Swedish Research Council (VR) [642-2013-8020]; KAW Fellowship/Scholar program

MXenes are technologically interesting 2D materials that show potential in numerous applications. The properties of the MXenes depend at large extent on the selection of elements that build the 2D MX-layer. Another key parameter for tuning the attractive material properties is the species that terminate the surfaces of the MX-layers. Although being an important parameter, experimental studies on the bonding between the MX-layers and the termination species are few and thus an interesting subject of investigation. Here we show that the termination species fluorine (F) bonds to the T3C2-surface mainly through Ti 3p – F 2p hybridization and that oxygen (O) bonds through Ti 3p – O 2p hybridization with a significant contribution of Ti 3d and Ti 4p. The study further shows that the T3C2-surface is not only terminated by F and O on the threefold hollow face-centered-cubic (fcc) site. A significant amount of O sits on a bridge site bonded to two Ti surface atoms on the T3C2-surface. In addition, the results provide no support for hydroxide (OH) termination on the T3C2-surface. On the contrary, the comparison of the valence band intensity distribution obtained through ultraviolet- and x-ray photoelectron spectroscopy with computed spectra by density of states, weighed by matrix elements and sensitivity factors, reveals that OH cannot be considered as a inherent termination species in Ti3C2Tx. The results from this study have implications for correct modeling of the structure of MXenes and the corresponding materials properties. Especially in applications where surface composition and charge are important, such as supercapacitors, Li-ion batteries, electrocatalysis, and fuel- and solar cells, where intercalation processes are essential., Funding agencies: Proposals 20190625, 20191107, and 20200582, the Swedish ResearchCouncil under contract 2018-07152, the Swedish Governmental Agency for Innovation Systems under contract 2018-04969, and Formas under contract 2019-02496, the Swedish Research Council through Grant Agreement No.2016-07213, the Swedish Research Council (VR) LiLi-NFM Linnaeus Environmentand Project Grant No. 621-2009-5258, the SwedishGovernment Strategic Research Area in Materials Science on Functional Materials at Linköping University (Faculty Grant SFO-Mat-LiU No. 2009-00971), the Swedish Energy Research (GrantNo. 43606-1) and the Carl Tryggers Foundation (CTS16:303,CTS14:310, CTS20:272).

Braze clad on aluminum (Al) sheets has enabled fast and convenient brazing assembly of complex heat exchangers. However, there are details in the brazing process that are not fully understood. Herein, 3D X-ray diffraction (3DXRD) is used to investigate the grain position, size, and orientation before and after controlled atmosphere brazing (CAB). The outcomes are presented as maps of center-of-mass positions with relative grain size distribution and color-coded grain orientations. The results show that, for braze clad Al sheets exposed to CAB simulation, it is possible to distinguish grains from the solidified Al-Si alloy from those in the core Al alloy. It is also possible to distinguish new grains obtained through recrystallization during CAB. Hence, the study shows that stretching of the rolled Al sheet by 6% provides enough stored energy in the core material so that recrystallization occurs during CAB and, in addition, provides conditions for Al-Si alloy grain growth into the core material. While the phenomenon is well known, it is poorly understood for processes in connection with brazing of mechanically formed Al alloy components in heat exchanger assemblies, and these results demonstrate the potential for gaining deeper insights through 3DXRD., Funding Agencies|Swedens Innovation Agency (Vinnova)Vinnova [2018-03268, 2019-05299]; QIM project at Lund University

We deposit CSx thin solid films by reactive direct current magnetron sputtering of a C target in an argon plasma, using carbon disulfide (CS2) as a precursor to film growth. We investigate the influence of the partial pressure of the CS2 vapor introduced into the plasma on the composition, the chemical bonding structure, the structural, and the mechanical properties as determined by x-ray photoelectron spectroscopy (XPS), Raman spectroscopy, scanning electron microscopy (SEM), and nanoindentation for films deposited at 150 and 300 degrees C. The Raman and the XPS results indicate that S atoms are incorporated in mostly sp(2) bonded C network. These results agree with previous ab-initio theoretical findings obtained by modeling of the CSx compound by the Synthetic Growth Concept. The microstructure of the films as well as the results of their Raman characterization and the nano mechanical testing results all point out that with the increasing S content some spa bonding is admixed in the predominantly sp(2) bonded CSx network, leading to typical amorphous structure with short and interlocked graphene-like planes for S contents between 2% and 8%. We conclude that CSx thin solid films deposited by using CS2 as a precursor would be CSx films deposited at low temperature of similar to 150 degrees C and with an S content in the region of 6 at.% may be interesting candidates for applications as hard/elastic protective coatings., Funding Agencies|Swedish Government Strategic Research Area in Materials Science on Advanced Functional Materials at Linkoping University [SFO-Mat-LiU 2009-00971]; Swedish Research Council (VR) through FLAG-ERA JTC 2015 project GRIFONESwedish Research Council [VR 2015-06816, VR 2017-04071]; Aforsk grant [18-266]; VRSwedish Research Council [VR 2016-05362]; Knut and Alice Wallenberg (KAW) FoundationKnut & Alice Wallenberg Foundation [KAW 2015.0043]

The inherently nanolaminated Ti3AlC2 is one of the most studied MAX-phase materials. MAX-phases consists of two-dimensional Mn+1Xn-layers (e.g., T3C2-layers) with strong internal covalent bonds separated by weakly interacting A-layers (e.g., Al-layers), where the repetitive stacking of the Mn+1Xn-layers and the A-layers suggests being the foundation for the unusual but attractive material properties of the MAX-phases. Although being an important parameter, the nature of the bonding between the Mn+1Xn-layers and the A-layers has not yet been established in detail. The X-ray photoelectron spectroscopy data presented in this paper suggest that the weak interaction between the Ti3C2-layers and the Al-layers in Ti3AlC2 is through electrostatic attraction facilitated by a charge redistribution of the delocalized electrons from the Ti3C2-layers to the Al-layers. This charge redistribution is of the same size and direction as between Ti atoms and Al atoms in TiAl alloy. This finding opens up a pathway to predict and improve MAX-phase materials properties through A-layer alloying, as well as to predict new and practically feasible MXene compounds., Funding Agencies|Swedish Foundation for Strategic Research (SSF)Swedish Foundation for Strategic Research [EM160004]; Swedish Research Council (VR)Swedish Research Council [6422013-8020]; KAW Fellowship/Scholar program

(Ti1-xAlx)B2+Delta films with a lateral composition gradient of x = [0.30-0.66] and Delta = [0.07-1.22] were deposited on an Al2O3 wafer by dual magnetron sputtering at 400 degrees C from sintered TiB2 and AlB2 targets. Composition analysis indicates that higher Ti:Al ratios favor overstoichiometry in B and a reduced incorporation of O. Transmission electron microscopy reveals distinctly different microstructures of Ti- and Al-rich compositions, with formation of characteristic conical growth features for the latter along with a lower degree of crystallinity and significantly less tissue phase from B segregation at the grain boundaries. For Al-rich films, phase separation into Ti- and Al-rich diboride nanometer-size domains is observed and interpreted as surface-initiated spinodal decomposition. The hardness of the films ranges from 14 to 28 GPa, where the higher values were obtained for the Ti-rich regions of the metal boride., Funding Agencies|Knut and Alice Wallenbergs (KAW) Foundation [KAW 2015.0043]; Swedish Research Council [330-2014-6336, 2016-04412, 642-2013-8020]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009 00971]; Marie Sklodowska Curie Actions COFUND [INCA 600398]; Swedish Foundation for Strategic Research; Research Infrastructure Fellow Program [RIF 14-0074]; KAW Foundation

Global warming caused by burning of fossil fuels is indisputably one of mankinds greatest challenges in the 21st century. To reduce the ever-increasing CO2 emissions released into the atmosphere, dry solid adsorbents with large surface-to-volume ratio such as carbonaceous materials, zeolites, and metal-organic frameworks have emerged as promising material candidates for capturing CO2. However, challenges remain because of limited CO2/N-2 selectivity and long-term stability. The effective adsorption of CO2 gas (approximate to 12 mol kg(-1)) on individual sheets of 2D transition metal carbides (referred to as MXenes) is reported here. It is shown that exposure to N-2 gas results in no adsorption, consistent with first-principles calculations. The adsorption efficiency combined with the CO2/N-2 selectivity, together with a chemical and thermal stability, identifies the archetype Ti3C2 MXene as a new material for carbon capture (CC) applications., Funding Agencies|Swedish Research Council [2016-04412, 2016-00889, 642-2013-8020]; Knut and Alice Wallenbergs Foundation [KAW 2015.0043]; Swedish Foundation for Strategic Research (SSF) [EM16-0004, RIF 14-0074, FL12-0181]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]

tThe chemical bonding in the carbide core and the surface chemistry in a new group of transition-metalcarbides Tin+1Cn-Tx(n = 1,2) called MXenes have been investigated by surface-sensitive valence bandX-ray photoelectron spectroscopy. Changes in band structures of stacked nano sheets of different thick-nesses are analyzed in connection to known hybridization regions of TiC and TiO2that affect elastic andtransport properties. By employing high excitation energy, the photoelectron cross-section for the C 2s– Ti 3d hybridization region at the bottom of the valence band is enhanced. As shown in this work, theO 2p and F 2p bands strongly depend both on the bond lengths to the surface groups and the adsorptionsites. The effect of surface oxidation and Ar+sputtering on the electronic structure is also discussed.

Thin films of (Ti0.71Al0.29)B2+1.08 have been deposited by magnetron sputtering. Post-deposition annealing at 1000 degrees C for 1 h results in increased hardness and elastic modulus, from 32 to 37 GPa and from 436 to 461 GPa, respectively. In both as-deposited and annealed states the films adhere well to the substrate, indicating no considerable internal stress. The initial high hardness is attributed to a columnar microstructure consisting of crystalline (Ti,Al)B-2 columns separated by an amorphous B matrix. The observed age hardening corresponds to phase separation within the (Ti,Al)B-2 columns including the formation of Ti-deficient crystallites within the grain interior upon annealing. (C) 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved., Funding Agencies|European Research Council under the European Community Seventh Framework Program (FP7)/ERC [258509]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [200900971]; Swedish Research Council (VR) [621-2012-4425, 642-2013-8020, 621-2011-4417, 330-2014-6336, 622-2008-405, 621-2012-4359]; SSF synergy grant FUNCASE; Knut and Mice Wallenberg (KAW) Foundation [2015.0043]

A theoretical and experimental study on the growth and properties of a ternary carbon-based material, CSxFy, synthesized from SF6 and C as primary precursors is reported. The synthetic growth concept was applied to model the possible species resulting from the fragmentation of SF6 molecules and the recombination of S-F fragments with atomic C. The possible species were further evaluated for their contribution to the film growth. Corresponding solid CSxFy thin films were deposited by reactive direct current magnetron sputtering from a C target in a mixed Ar/SF6 discharge with different SF6 partial pressures (P-SF6). Properties of the films were determined by x-ray photoelectron spectroscopy, x-ray reflectivity, and nanoindentation. A reduced mass density in the CSxFy films is predicted due to incorporation of precursor species with a more pronounced steric effect, which also agrees with the low density values observed for the films. Increased P-SF6 leads to decreasing deposition rate and increasing density, as explained by enhanced fluorination and etching on the deposited surface by a larger concentration of F/F-2 species during the growth, as supported by an increment of the F relative content in the films. Mechanical properties indicating superelasticity were obtained from the film with lowest F content, implying a fullerene-like structure in CSxFy compounds., Funding Agencies|Swedish Foundation for Strategic Research (SSF) Synergy Grant on Functional Carbides and Advanced Surface Engineering (FUNCASE) [RMA11-0029]; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University [2009-00971]

The high plasma density and large fraction of ionized species created in a high power impulse magnetron sputtering (HiPIMS) discharge add new measures to control the sputtering process. We have studied the sputtering of TiB2 coatings by HiPIMS from a compound target in an industrial system. How the degree of ionized species effects coating microstructure and mechanical properties has been investigated by varying the pulse frequency between 200 Hz and 1000 Hz while keeping the average power constant at 2 kW. The coatings have a B/Ti atomic ratio amp;gt;= 2.5 and a microstructure exhibiting 001 textured nanocolumnar grains with an amorphous B tissue phase in grain boundaries. Lower frequencies provide higher degree of ionization, which does, however, increase the compressive residual stress in the coatings. This results in harder coatings and the highest hardness of 49 GPa is measured for the coating deposited at 200 Hz (-3.8 GPa residual stress). A change in texture from random orientation to 001 texture is achieved when going from regular dc sputtering to HiPIMS at a floating bias. Superhard (H = 43 GPa) TiB2 coatings with a relatively low compressive stress of about -1 GPa can be deposited by HiPIMS at 1000 Hz using floating bias. (C) 2016 Elsevier B.V. All rights reserved., Funding Agencies|Knut and Alice Wallenberg Foundation [2015.0043]; Electron Microscopy laboratory in Linkoping; Swedish Research Council (VR) [642-2013-8020, 622-2008-405, 621-2012-4359]

A new carbon-based compound: CSxFy was addressed by density functional theory calculations and synthesized by reactive magnetron sputtering. Geometry optimizations and energy calculations were performed on graphene-like model systems containing sulfur and fluorine atoms. It is shown that [S+F] concentrations in the range of 0−10 at.%, structural ordered characteristics similar to graphene pieces containing ring defects are energetically feasible. The modeling predicts that CSxFy thin films with graphite and fullerene-like characteristics may be obtained for the mentioned concentration range. Accordingly, thin films were synthesized from a graphite solid target and sulfur hexafluoride as reactive gas. In agreement with the theoretical prediction, transmission electron microscopy characterization and selected area electron diffraction confirmed the presence of small ordered clusters with graphitic features in a sample containing 0.4 at.% of S and 3.4 at.% of F., funding agencies: Swedish Foundation for Strategic Research (SSF) [RMA11-0029]; Carl Trygger Foundation for Scientific Research; Swedish Research Council [642-2013-8020]; ERC [258509]; Knut and Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Materials at Linkoping University Vid tiden för disputation förelåg publikationen som manuskript

We present an industry-relevant, large-scale, ultra-high vacuum (UHV) magnetron sputtering and cathodic arc deposition system purposefully designed for time-resolved in situ thin film deposition/annealing studies using high-energy (greater than50 keV), high photon flux (greater than10(12) ph/s) synchrotron radiation. The high photon flux, combined with a fast-acquisition-time (less than1 s) two-dimensional (2D) detector, permits time-resolved in situ structural analysis of thin film formation processes. The high-energy synchrotron-radiation based x-rays result in small scattering angles (less than11 degrees), allowing large areas of reciprocal space to be imaged with a 2D detector. The system has been designed for use on the 1-tonne, ultra-high load, high-resolution hexapod at the P07 High Energy Materials Science beamline at PETRA III at the Deutsches Elektronen-Synchrotron in Hamburg, Germany. The deposition system includes standard features of a typical UHV deposition system plus a range of special features suited for synchrotron radiation studies and industry-relevant processes. We openly encourage the materials research community to contact us for collaborative opportunities using this unique and versatile scientific instrument. (C) 2015 AIP Publishing LLC., Funding Agencies|Swedish Research Council via the Rontgen Angstrom Cluster (RAC) Frame Program [2011-6505]; German Federal Ministry of Education and Research (BMBF) [05K12CG1]

Following our recent discovery of a new nanolaminated carbide, Mo2Ga2C, we herein present a detailed structural and chemical analysis of this phase based on ab initio calculations, X-ray photoelectron spectroscopy, high resolution scanning transmission electron microscopy, and neutron powder diffraction. Calculations suggest an energetically and dynamically stable structure for C in the octahedral sites between the Mo layers, with Ga bilayers - stacked in a simple hexagonal arrangement - between the Mo2C layers. The predicted elastic properties are below those of the related nanolaminate Mo2GaC. The predicted structure, including lattice parameters and atomic positions, is experimentally confirmed. (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved., Funding Agencies|Swedish Research Council [621-2011-4420, 642-2013-8020, 621-2014-4890]; Swedish Foundation for Strategic Research through the Synergy Grant FUNCASE Functional Carbides for Advanced Surface Engineering; Future Research Leaders 5 Program; ERC [258509]; Knut and Alice Wallenberg Foundation

We report on the synthesis of a two-dimensional transition metal carbide, Mo2C, (MXene) obtained by immersing Mo2Ga2C thin films in hydrofluoric acid. Experimental evidences for neither synthesis of a Mo-based MXene nor selective etching of Ga from an atomic nanolaminate have previously been presented. MXene formation is verified through X-ray diffraction, transmission electron microscopy, and energy dispersive X-ray spectroscopy. This discovery unlocks new potential applications for Mo-based MXenes in a host of applications, from thermoelectrics to catalysis and energy storage.

We have studied the utilization of TiB2 cathodes for thin film deposition in a DC vacuum arc system. We present a route for attaining a stable, reproducible, and fully ionized plasma flux of Ti and B by removal of the external magnetic field, which leads to dissipation of the vacuum arc discharge and an increased active surface area of the cathode. Applying a magnetic field resulted in instability and cracking, consistent with the previous reports. Plasma analysis shows average energies of 115 and 26 eV, average ion charge states of 2.1 and 1.1 for Ti and B, respectively, and a plasma ion composition of approximately 50% Ti and 50% B. This is consistent with measured resulting film composition from X-ray photoelectron spectroscopy, suggesting a negligible contribution of neutrals and macroparticles to the film growth. Also, despite the observations of macroparticle generation, the film surface is very smooth. These results are of importance for the utilization of cathodic arc as a method for synthesis of metal borides. (C) 2015 AIP Publishing LLC., Funding Agencies|European Research Council under the European Community Seventh Framework Program (FP7)/ERC [258509]; Swedish Research Council (VR) [642-2013-8020]; Knut and Alice Wallenberg Foundation; SSF synergy grant FUNCASE

Since the discovery of graphene, the quest for two-dimensional (2D) materials has intensified greatly. Recently, a new family of 2D transition metal carbides and carbonitrides (MXenes) was discovered that is both conducting and hydrophilic, an uncommon combination. To date MXenes have been produced as powders, flakes, and colloidal solutions. Herein, we report on the fabrication of similar to 1 x 1 cm(2) Ti3C2 films by selective etching of Al, from sputter-deposited epitaxial Ti3AlC2 films, in aqueous HF or NH4HF2. Films that were about 19 nm thick, etched with NH4HF2, transmit similar to 90% of the light in the visible-to-infrared range and exhibit metallic conductivity down to similar to 100 K. Below 100 K, the films resistivity increases with decreasing temperature and they exhibit negative magnetoresistance-both observations consistent with a weak localization phenomenon characteristic of many 2D defective solids. This advance opens the door for the use of MXenes in electronic, photonic, and sensing applications.

The catalytic and durable electrode coating of ruthenium dioxide (RuO2), applied on nickel (Ni) substrates, is today utilized as electrocatalytic cathodes for hydrogen production, e.g., in the chlor-alkali process and alkaline water electrolysis. The drawback is, however, the sensitivity to reverse currents obtained during power shutdowns, e.g., at maintenance, where the RuO2-based electrodes can be severely damaged unless polarization rectifiers are employed. Through the material characterization techniques X-ray diffraction and X-ray photoelectron spectroscopy, we can now reveal that RuO2 coatings, when exposed to hydrogen evolution at industrially relevant conditions, transforms into ruthenium oxyhydroxide (RuO(OH)(2)). The study further shows that as the hydrogen evolution proceeds the formed RuO(OH)(2) reduces to metallic ruthenium (Ru).

Carbon and carbon nitride films (CNx , 0 ≤ x ≤ 0.26) were deposited by filtered pulsed cathodic arc and were investigated using transmission electron microscopy and X-ray photoelectron spectroscopy. A “fullerene-like” (FL) structure of ordered graphitic planes, similar to that of magnetron sputtered FL-CNx films, was observed in films deposited at 175 °C and above, with N2 pressures of 0 and 0.5 mTorr. Higher substrate temperatures and significant nitrogen incorporation are required to produce similar FL structure by sputtering, which may, at least in part, be explained by the high ion charge states and ion energies characteristic of arc deposition. A gradual transition from majority sp3-hybridized films to sp2 films was observed with increasing substrate temperature. High elastic recovery, an attractive characteristic mechanical property of FL-CNx films, is evident in arc-deposited films both with and without nitrogen content, and both with and without FL structure.

A reverse current obtained during power shutdowns in industrial processes, such as chlor-alkali production or alkaline water electrolysis, is deleterious for hydrogen evolving ruthenium dioxide (Ru02) based cathodes. It has been observed that RuO2 coatings after a power shutdown, necessary for e.g. maintenance, are severely damaged unless polarization rectifiers are employed. In this work we show why these types of cathodes are sensitive to reverse currents, i.e. anodic currents, after hydrogen evolution. RuO2 coatings deposited on nickel substrates were subjected to different electrochemical treatments such as hydrogen evolution, oxygen evolution, or reverse currents in 8 M NaOH at 90 degrees C. Polarity inversion was introduced after hydrogen evolution to simulate the effect of reverse currents. Because of chemical interaction with hydrogen, a significant amount of the RuO2 coating was transformed into hydroxylated species during cathodic polarization. Our study shows that these hydroxylated phases are highly sensitive to electrochemical corrosion during anodic polarization after extended hydrogen evolution., Funding Agencies|Swedish Research Council [2007-5059]; European Research Council under the European Communities/ERC [258509]; Swedish Research Council (VR) [642-2013-8020]; KAW Fellowship program

The formation of water through hydrogenation of oxygen on platinum occurs at a surprisingly low reaction rate. The reaction rate limited process for this catalytic reaction is, however, yet to be settled. In the present work, the reaction rates of the first and the second hydrogen addition steps are compared when hydrogen is obtained through intense synchrotron radiation that induces proton production in a water overlayer on top of the adsorbed oxygen species. A substantial amount of the produced hydrogen diffuses to the platinum surface and promotes water formation at the two starting conditions O/Pt(111) and (H 2O+OH)/Pt(111). The comparison shows no significant difference in the reaction rate between the first and the second hydrogen addition steps, which indicates that the rate determining process of the water formation from oxygen on Pt(111) is neither the first nor the second H addition step or, alternatively, that both H addition steps exert rate control. © 2014 AIP Publishing LLC.

Herein, we report X-ray Photoelectron Spectroscopy (XPS) analysis for cold pressed exfoliated 2D nanocrystals of transition metal carbides, MXenes. MXenes are a recently discovered family of 2D materials produced by selective chemical etching of the A element from MAX phases which are ternary metal carbides and nitrides. The latter has the formula of Mn+1AXn, where M is an early transition metal, A is an A-group element, and X is C and/or N. This study is a comparison between two MXenes, Ti3C2Tx and Ti2CTx, where Tx stands for surface termination groups such as –O, –OH, and –F. Ti3C2Tx and Ti2CTx were prepared by immersion of Ti3AlC2 and Ti2AlC powders in 50% conc. HF. A thorough XPS analysis was performed through peak fitting of high resolution XPS spectra and valence band, VB, spectra analysis. The effect of Ar sputtering as well as the number of layers n was the primarily interest of this study. According to the peak fitting analysis, both phases contain the following species, Ti–C, C–C, Ti–F, Ti–O and Ti–OH resulting in the following chemical formulas: Ti3C2(OH)x(O)y(F)z and Ti2C(OH)x(O)y(F)z. Comparing the VB spectra with the DOS calculations show the valance band spectra is actually a mixture of MXene with various terminations of OH, O and F. Before Ar+ sputtering both phases show a large percentage of fluorinated-TiO2 which is due to MXene surface oxidation as well as CHx, C-O and COO groups arising from either surface contaminations or due to drying the etched powders in ethanol after washing the powder of the HF acid. According to the VB spectra, it is shown that the fluorinated TiO2 is actually a mixture of anatase and rutile. The number of layers, n, also plays a role; the lower n, the more the MXene is prone to oxidation.

Electrochemical water splitting into H2 and O2 presents a significant and challenging energy loss due to the high overpotential required at the anode. Today, in industrially relevant applications, dimensionally stable anodes (DSA) based on the electrocatalytic active RuO2 are conventionally utilized. To enhance the resistance against corrosion, incorporation of TiO2 in the RuO2-coated electrodes is widely employed. In the present work we have used scanning electrochemical microscopy (SECM) to demonstrate that TiO2-doped RuO2-coated electrodes, in addition to being more durable, also show an electrocatalytic activity that is, on average, 13% higher as compared to the pure RuO2-coated electrodes. We also demonstrate that cracks in the pure RuO2 coating are the most active zones, probably because Ti from the Ti support has diffused into the first applied layer of the RuO2 coating. To reveal the nature of this enhanced activity for water oxidation displayed on TiO2-doped RuO2 electrodes, we have employed X-ray photoelectron spectroscopy (XPS) for material characterization. The results show that the electrocatalytic activity enhancement displayed on the mixed (Ru1−x:Tix)O2 coating is promoted through a charge transfer from the RuO2 to the TiO2, which provides new and more reactive sites designated as activated RuO2δ+., Publication Date (Web): February 11, 2013

Oxygen hydrogenation under ultra high vacuum conditions at the platinum surface was explored using temperature-programmed X-ray photoelectron spectroscopy. Through modeling of the oxygen consumption, information on the reaction kinetics was obtained indicating that the reaction rate of the oxygen hydrogenation process depends on the hydrogen diffusion and on the lifetime of hydroxyl intermediates. The reaction rate is, however, enhanced when an autocatalytic process stabilizes the hydroxyl intermediates through hydrogen bonding to neighboring water molecules. The overall activation energy for the hydrogenation of atomic oxygen to form water was determined to be 0.20 eV with a frequency factor of only 10(3) s(-1)., Funding Agencies|Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering|DE-AC02-76SF00515