TY - JOUR A1 - You, Yi A1 - Song, L. A1 - Young, M.D. A1 - van der Wielen, M. A1 - Evans-Nguyen, T. A1 - Riedel, Jens A1 - Shelley, J.T. T1 - Unsupervised Reconstruction of Analyte-Specific Mass Spectra Based on Time-Domain Morphology with a Modified Cross-Correlation Approach N2 - Concomitant species that appear at the same or very similar times in a mass-spectral analysis can clutter a spectrum because of the coexistence of many analyte-related ions (e.g., molecular ions, adducts, fragments). One method to extract ions stemming from the same origin is to exploit the chemical information encoded in the time domain, where the individual temporal appearances inside the complex structures of chronograms or chromatograms differ with respect to analytes. By grouping ions with very similar or identical time-domain structures, single-component mass spectra can be reconstructed, which are much easier to interpret and are library-searchable. While many other approaches address similar objectives through the Pearson’s correlation coefficient, we explore an alternative method based on a modified cross-correlation algorithm to compute a metric that describes the degree of similarity between features inside any two ion chronograms. Furthermore, an automatic workflow was devised to be capable of categorizing thousands of mass-spectral peaks into different groups within a few seconds. This approach was tested with direct mass-spectrometric analyses as well as with a simple, fast, and poorly resolved LC–MS analysis. Single-component mass spectra were extracted in both cases and were identified based on accurate mass and a mass-spectral library search. KW - Mass-Spectral Reconstruction KW - Mass Spectrometry KW - Correlation PY - 2021 DO - https://doi.org/10.1021/acs.analchem.0c04396 VL - 93 IS - 12 SP - 5009 EP - 5014 PB - ACS AN - OPUS4-52467 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xue, Boyang A1 - You, Yi A1 - Gornushkin, Igor B. A1 - Zheng, R. A1 - Riedel, Jens T1 - High-throughput underwater elemental analysis by μJ-laser-induced breakdown spectroscopy at kHz repetition rates: part I, ultrasound-enhanced optical emission spectroscopy towards application perspectives N2 - In recent years, laser-induced breakdown spectroscopy (LIBS) has gained significant attention as a means for simple elemental analyses. The suitability of LIBS for contactless analysis allows it to be a perfect candidate for underwater applications. While the majority of LIBS systems still rely upon sub-kHz pulsed lasers, this contribution introduces 10s-kHz low pulse-energy lasers into underwater LIBS to improve the throughput and statistical validity. Interestingly, the spectral component significantly changed above a critical laser repetition-rate threshold. Spectral lines of atomic hydrogen and oxygen stemming from water become visible beyond a ∼10 kHz repetition rate. This observation suggests a different plasma dynamic compared to low repetition rates. When the pulse-to-pulse interval becomes sufficiently short, a cumulative effect begins to be significant. Apparently, the new phenomena occur on a timescale corresponding to a threshold rate of ∼10 kHz, i.e. ∼100 μs. Analytically, the high repetition rates result in improved statistical validity and throughput. More plasma events per unit time allowed the use of low efficiency Echelle spectrometers without compromising on the analytical performance. Meanwhile, the presence of H I and O I out of the water (as the matrix) also offers internal standardization in underwater elemental analysis. Since the laser fluence was on the lower edge of the plasma threshold, an additional ultrasound source was introduced to induce external perturbation, which significantly improved the plasma formation stability. A huge advantage of LIBS is the possibility of detecting almost all elements within a sample simultaneously. Throughout the periodic table, chlorine is one of the most challenging elements. Consequently, Ca2+ and Na+ were used as samples to demonstrate the capability of this high repetition-rate LIBS platform. As an ambitious benchmark for our system, chlorine detection in water was also discussed. KW - High repetition rate KW - Laser-induced breakdown spectroscopy PY - 2020 DO - https://doi.org/10.1039/D0JA00290A VL - 35 IS - 12 SP - 2901 EP - 2911 PB - The Royal Society of Chemistry AN - OPUS4-51564 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Xue, Boyang A1 - You, Yi A1 - Riedel, Jens T1 - High-throughput underwater elemental analysis by μJ-laser-induced breakdown spectroscopy at a kHz repetition rate: part II, understanding the high repetition-rate from a fundamental perspective N2 - The technological advances in lasers enabled the wide application of laser-induced breakdown spectroscopy (LIBS) as a powerful analytical means for elemental analyses. Rather than commonly used lasers that operate at several to several-tens of Hz, the high repetition rate ones that operate at tens of kHz showed superior analytical advantages while implying unique excitation pathways. Specifically, the production of excited atomic hydrogen and oxygen, which can serve as internal standards, is quite different from that in commonly reported double-pulse LIBS. In this part of the work, it was found that the atomic emitters stemming from water are not related to cavitation bubbles. Moreover, the emitter productions of dissolved species, e.g., Na+, and water-related species, e.g., H-α, are two distinctive mechanisms. Towards analytical applications of the high repetition-rate system, the fundamental investigation can provide important guidelines to address real-life challenges. In this part of the work, the high repetition-rate regime of operation is explored from a more kinetic perspective. KW - High repetition rate KW - Laser-induced breakdown spectroscopy PY - 2020 DO - https://doi.org/10.1039/D0JA00291G VL - 35 IS - 12 SP - 2912 EP - 2919 PB - Royal Society of Chemistry AN - OPUS4-51565 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Chinellato, Fabio A1 - Wilbig, Janka A1 - Al-Sabbagh, Dominik A1 - Colombo, P. A1 - Günster, Jens T1 - Gas flow assisted powder deposition for enhanced flowability of fine powders: 3D printing of alpha-tricalcium phosphate N2 - The possibility of creating patient-specific individual implants makes Additive Manufacturing technologies of special interest for the medical sector. For substitution of bone defects, powder based Additive Manufacturing by Binder Jetting is a suitable method to produce complex scaffold-like structures made of bioceramics with easily adapted geometries and controlled porosity. The process inherent residual porosity in the printed part, even though desired as it supports bone ingrowth, also leads to limited mechanical strength. Currently, bioceramic scaffolds made by Binder Jetting feature suitable biocompatible and biodegradable properties, while a sufficient mechanical stability is rather challenging. The purpose of this work is to apply the gas flow assisted powder deposition introduced in 2014 by Zocca et al., to the powder bed during printing of bioceramic tablets and scaffolds using α-TCP powder as feedstock. This enables exploiting the advantages of an increased powder bed density, thereby improving the mechanical properties of the printed parts. KW - Additive Manufacturing KW - Binder Jetting KW - Gas flow assisted powder deposition KW - Alpha-tricalcium phosphate KW - Scaffold PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-510138 DO - https://doi.org/10.1016/j.oceram.2020.100003 SN - 2666-5395 VL - 1 SP - 100003 PB - Elsevier Ltd. AN - OPUS4-51013 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Durlo Tambara, Luís Urbano A1 - Nikoonasab, Ali A1 - Radtke, Martin A1 - de Oliveira Guilherme Buzanich, Ana A1 - Gluth, Gregor T1 - Determination of the oxidation depths of ground granulated blast furnace slag-containing cement pastes using Mn K-edge X-ray absorption near-edge structure spectroscopy N2 - The redox potential of the pore solution of hardened cements containing ground granulated blast furnace slag (GGBFS) affects reinforcement corrosion and immobilization of radioactive waste. Here, Mn K-edge X-ray absorption near-edge structure (XANES) spectroscopy was applied to determine the depth profile of the oxidation state of manganese in hardened GGBFS-containing cement pastes. Manganese was oxidized in the outer regions of some of the pastes, but the depth to which this occurred was not identical with the ‘blue-green/white color change front’, usually interpreted as indicating oxidation of sulfur species. For CEM III/B, the color change of the material was gradual and thus unsuitable for a precise determination of the oxidation depth, while for the alkali-activated slag, a distinct color change front was found, but full oxidation of manganese and sulfur had not occurred in the brighter region. Mn K-edge XANES spectroscopy is thus a more reliable method than the determination of the visual color change front to follow the ingress of the oxidation front. KW - Manganese KW - Oxidation KW - Sulfide KW - Alkali-activated materials KW - Redox conditions PY - 2026 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-651469 DO - https://doi.org/10.1111/jace.70445 SN - 0002-7820 SN - 1551-2916 VL - 109 IS - 1 SP - 1 EP - 11 PB - Wiley CY - Oxford AN - OPUS4-65146 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Stephan, Jenny A1 - Stühler, Merlin R. A1 - Fornacon-Wood, Christoph A1 - Dimde, Mathias A1 - Ludwig, Kai A1 - Sturm, Heinz A1 - Olmedo-Martínez, Jorge L. A1 - Müller, Alejandro J. A1 - Plajer, Alex J. T1 - Sulfur-containing block polymers from ring-opening copolymerization: coordinative encapsulants for transition metals N2 - Sulfur-containing polymers can coordinate transition metals via sulfur-centered, chemically soft lone pairs, although this typically occurs in a spatially uncontrolled manner. In this study, we employed the controlled ring-opening copolymerization of oxetane with sulfur-containing comonomers to construct a series of amphiphilic block copolymers featuring thioester and thiocarbonate functionalities. These copolymers self-assemble in aqueous solution into aggregates with a sulfur-rich core capable of coordinating transition metals. This behavior could be resolved by employing cryo-transmission electron tomography and then extended to complexes incorporating functional coligands. Our study demonstrates how selective catalysis can be harnessed to produce functional polymers with tunable metal coordination properties, paving the way for an emerging class of sulfur-containing copolymers. KW - Sulfur-containing polymer KW - Controlled synthesis KW - Metal ion coordination KW - Cryo TEM PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-626157 DO - https://doi.org/10.1039/d4py01415d SN - 1759-9962 VL - 16 IS - 8 SP - 1003 EP - 1009 PB - Royal Society of Chemistry (RSC) AN - OPUS4-62615 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Yao, Xingyu A1 - Antunes, Margarida M. A1 - Guilherme Buzanich, Ana A1 - Cabanelas, Pedro A1 - Valente, Anabela A. A1 - Pinna, Nicola A1 - Russo, Patrícia A. T1 - Formation, Phase Transition, Surface, and Catalytic Properties of Cubic ZrO 2 Nanocrystals N2 - Pseudocapacitance-type transition metal oxides have been extensively investigated as anodes for lithium-ion batteries (LIBs). Currently, they are also gaining attention for sodium-ion batteries (SIBs) due to their low volume change and safety. However, their performance in sodium storage remains limited, primarily due to the larger Na+ ion radius. Here, for the first time, an iron niobate is reported with a columbite structure as a high-Performance sodium storage anode. The presence of iron triggers the loss of long-rangeorder through disorder of the FeO6 octahedra local structure, subsequentlyallowing reversible sodium storage in an amorphous phase. Simultaneously, the formation of short-range ordered zigzag-chain structures within the NbO6 planes creates a “skeleton” that offers abundant active sites forpseudocapacitive ion storage and enhanced ion diffusion pathways. These characteristics of FeNb2O6 make it an effective intercalation host, offering high capacity along with fast Na+ kinetics, as demonstrated through operando and ex situ characterizations. It leads to an applicable reversible capacity (>300 mAh g−1) with a favorable average voltage of ≈0.6 V and excellent rate capability (180.4 mAh g−1 at a current density of 2 A g−1). This study provides insights into the development of intrinsically active transition metal oxides for Na+-ion intercalation. KW - XAS KW - Sodium-ion Batteries PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654955 DO - https://doi.org/10.1021/acs.chemmater.5c01483 SN - 0897-4756 VL - 37 IS - 21 SP - 8568 EP - 8580 PB - American Chemical Society (ACS) AN - OPUS4-65495 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Faustino, Leandro A. A1 - de Angelis, Leonardo D. A1 - de Melo, Eduardo C. A1 - Farias, Giliandro A1 - dos Santos, Egon C. A1 - Miranda, Caetano R. A1 - Buzanich, Ana G. A1 - Torresi, Roberto M. A1 - de Oliveira, Paulo F.M. A1 - Córdoba de Torresi, Susana I. T1 - Urea synthesis by Plasmon-Assisted N2 and CO2 co-electrolysis onto heterojunctions decorated with silver nanoparticles N2 - The N2 + CO2 co-electrolysis to urea synthesis has become a promising alternative to the energy intensive traditional processes for urea production. However, there are still challenges in this approach, especially due to the competition with HER (Hydrogen Evolution Reaction) leading to low efficiency. Electrochemistry assisted by localized surface plasmon resonance (LSPR) using metal nanoparticles has been reported to enhance different electrochemical reactions. Here we report an electrochemical LSPR assisted urea synthesis using Ag nanoparticles (NPs) supported on BiVO4/BiFeO3 catalyst mechanochemically synthesized. The electrochemical experiments were performed under dark and upon plasmon excitation at the LSPR region of Ag NPs. Our results demonstrated that exciting in the LSPR range, urea yield rate and Faradic efficiency were considerably improved with reduced overpotential, 19.2 μmol h− 1 g− 1 and FE 24.4% at +0.1 V vs RHE compared to 9.6 μmol h− 1 g− 1 and FE 9.4% at − 0.2 V vs RHE under dark conditions. Further in situ FTIR-RAS experiments for mechanism investigation revealed the presence of N-H and C-N intermediates and the real effect of Ag plasmon excitation on HER and N2 + CO2 co-electrolysis. Theoretical calculations confirm the energy of the species involved in C-N coupling as well the role of the complex catalytic sites, which agrees with XAS measurements. KW - Plasmon-assited KW - XAS KW - Urea KW - Electrocatalysis PY - 2025 DO - https://doi.org/10.1016/j.cej.2025.163072 SN - 1385-8947 VL - 513 SP - 1 EP - 13 PB - Elsevier B.V. AN - OPUS4-65492 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Liu, Yanchen A1 - Guilherme Buzanich, Ana A1 - Alippi, Paola A1 - Montoro, Luciano A. A1 - Lee, Kug‐Seung A1 - Jeon, Taeyeol A1 - Weißer, Kilian A1 - Karlsen, Martin A. A1 - Russo, Patrícia A. A1 - Pinna, Nicola T1 - FeNb 2 O 6 as a High‐Performance Anode for Sodium‐Ion Batteries Enabled by Structural Amorphization Coupled with NbO 6 Local Ordering N2 - Pseudocapacitance-type transition metal oxides have been extensively investigated as anodes for lithium-ion batteries (LIBs). Currently, they are also gaining attention for sodium-ion batteries (SIBs) due to their low volume change and safety. However, their performance in sodium storage remains limited, primarily due to the larger Na+ ion radius. Here, for the first time, an iron niobate is reported with a columbite structure as a high-performance sodium storage anode. The presence of iron triggers the loss of long-range order through disorder of the FeO6 octahedra local structure, subsequently allowing reversible sodium storage in an amorphous phase. Simultaneously, the formation of short-range ordered zigzag-chain structures within the NbO6 planes creates a “skeleton” that offers abundant active sites for pseudocapacitive ion storage and enhanced ion diffusion pathways. These characteristics of FeNb2O6 make it an effective intercalation host, offering high capacity along with fast Na+ kinetics, as demonstrated through operando and ex situ characterizations. It leads to an applicable reversible capacity (>300 mAh g−1) with a favorable average voltage of ≈0.6 V and excellent rate capability (180.4 mAh g−1 at a current density of 2 A g−1). This study provides insights into the development of intrinsically active transition metal oxides for Na+-ion intercalation. KW - SIB KW - XAS KW - Sodium-ion Batteries PY - 2025 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-654931 DO - https://doi.org/10.1002/adma.202504100 SN - 0935-9648 VL - 37 IS - 46 SP - 1 EP - 13 PB - Wiley AN - OPUS4-65493 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Bustos, Jenna A1 - Shohel, Mohammad A1 - Guilherme Buzanich, Ana A1 - Zakharov, Lev A1 - Buils, Jordi A1 - Segado‐Centellas, Mireia A1 - Bo, Carles A1 - Nyman, May T1 - Technetium and Rhenium Auto‐reduction, Polymerization and Lability towards Group VII Polyoxometalate Chemistry N2 - AbstractGroup VII Tc and Re have long been studied to develop both radiopharmaceuticals and technologies for nuclear materials management. Fundamental research has targeted understanding this periodic table crossroads where polyoxometalates meets metal‐metal bonded complexes. Here we have isolated green hygroscopic and metastable crystals of (ReVI,oct)2(ReVII,tet)2(OH)2(O)12⋅H2O (ReVI,VII‐green, tet=tetrahedral, oct=octahedral), determined by single‐crystal x‐ray diffraction. In addition to color, Re‐L1 X‐ray absorption near‐edge spectroscopy confirms the reduced oxidation state. ReVI,VII‐green provides the first demonstration of Re autoreduction, long‐observed for Mn and Tc. We also isolated and structurally characterized [Tc4O4(H2O)2(ReO4)14]2− (Tc4Re14) polyanion crystals that contain Tc(V) and Re(VII), consistent with greater stability of reduced Tc compared to reduced Re. Small angle X‐ray scattering of both compounds and prior‐reported polyanion [Tc4O4(H2O)2(TcO4)14]4− (Tc20) dissolved in acetonitrile indicated a qualitative lability order of oxo‐linkages of Re‐O−Re Re‐O−Tc Tc‐O−Tc, and lability of Tc20 was also probed by 99Tc nuclear magnetic resonance spectroscopy. Computation provided insight into 99Tc chemical shifts as well as lability. Based on both reducibility and solution phase dynamics of polynuclear compounds investigated here, Re is an imperfect surrogate for Tc, and further expansion of group VII polyoxometalate chemistry seems promising. KW - XANES KW - Polyoxometalate KW - Technetium PY - 2025 DO - https://doi.org/10.1002/chem.202404144 SN - 0947-6539 VL - 31 IS - 21 SP - 1 EP - 7 PB - Wiley-VCH Verl. AN - OPUS4-65491 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Nguyen, H. G. A1 - Toman, B. A1 - van Zee, R. A1 - Prinz, Carsten A1 - Thommes, M. A1 - Ahmad, R. A1 - Kiska, D. A1 - Salinger, J. A1 - Walton, I. A1 - Walton, K. A1 - Broom, D. A1 - Benham, M. A1 - Ansari, H. A1 - Pini, R. A1 - Petit, C. A1 - Adolphs, J. A1 - Schreiber, A. A1 - Shigeoka, T. A1 - Konishi, Y. A1 - Nakai, K. A1 - Henninger, M. A1 - Petrzik, T. A1 - Kececi, C. A1 - Martis, V. A1 - Paschke, T. A1 - Mangano, E. A1 - Brandani, S. T1 - Reference isotherms for water vapor sorption on nanoporous carbon: results of an interlaboratory study N2 - This paper reports the results of an international interlaboratory study sponsored by the Versailles Project on Advanced Materials and Standards (VAMAS) and led by the National Institute of Standards and Technology (NIST) on the measurement of water vapor sorption isotherms at 25 °C on a pelletized nanoporous carbon (BAM-P109, a certified reference material). Thirteen laboratories participated in the study and contributed nine pure water vapor isotherms and four relative humidity isotherms, using nitrogen as the carrier gas. From these data, reference isotherms, along with the 95% uncertainty interval (Uk=2), were determined and are reported in a tabular format. KW - BAM-P109 KW - Interlaboratory study KW - Nanoporous carbon KW - Reference isotherm KW - VAMAS PY - 2023 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-576560 DO - https://doi.org/10.1007/s10450-023-00383-1 SN - 0929-5607 SP - 1 EP - 12 PB - Springer CY - Heidelberg AN - OPUS4-57656 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER - TY - JOUR A1 - Kruschwitz, Sabine A1 - Halisch, M. A1 - Dlugosch, R. A1 - Prinz, Carsten T1 - Toward a better understanding of low-frequency electrical relaxation - An enhanced pore space characterization N2 - Relaxation phenomena observed in the electrical low-frequency range (approximately 1 mHz-10 kHz) of natural porous media like sandstones is often assumed to be directly related to the dominant (modal) pore throat sizes measured, for instance, with mercury intrusion porosimetry. Attempts to establish a universally valid relationship between pore size and peak Spectral Induced Polarization (SIP) relaxation time have failed, considering sandstones from very different origins and featuring great variations in textural and chemical compositions as well as in geometrical pore space properties. In addition working with characteristic relaxation times determined in Cole-Cole or Debye decomposition fits to build the relationship have not been successful. In particular, samples with narrow pore throats are often characterized by long SIP relaxation times corresponding to long “characteristic length scales” in these media, assuming that the diffusion coefficients along the electrical double layer were constant. Based on these observations, three different types of SIP relaxation can be distinguished. We present a new way of assessing complex pore spaces of very different sandstones in a multi-methodical approach to combine the benefits of mercury intrusion porosimetry, micro-computed tomography, and nuclear magnetic resonance. In this way, we achieve much deeper insight into the pore space due to the different resolutions and sensitivities of the applied methods to both pore constrictions (throats) and wide pores (pore bodies). We experimentally quantify pore aspect ratios and volume distributions within the two pore regions. We clearly observe systematic differences between three SIP relaxation types identified previously and can attribute the SIP peak relaxation times to measured characteristic length scales within our materials. We highlight selected results for a total of nine sandstones. It seems that SIP relaxation behavior depends on the size difference of the narrow pore throats to the wide pore bodies, which increases from SIP Type 1 to Type 3. KW - µ-CT KW - Spectral induced polarization KW - Nuclear magnetic resonance KW - Pore space PY - 2020 UR - https://nbn-resolving.org/urn:nbn:de:kobv:b43-509763 DO - https://doi.org/10.1190/GEO2019-0074.1 SN - 0016-8033 VL - 85 IS - 4 SP - MR257 EP - MR270 PB - Society of Exploration Geophysicists AN - OPUS4-50976 LA - eng AD - Bundesanstalt fuer Materialforschung und -pruefung (BAM), Berlin, Germany ER -