bluuebunny/crossref_metadata_2025_split huggingface dataset:
The on-Surface Supramolecular Chemistry of Porphyrins, Phthalocyanines and Sub-Phthalocyanines: How Shape and Functionalization Change the Game
Authors: Jung Thomas A. , Ahsan Aisha , Sk Rejaul , Heydari Mehdi , Baljozovic Milos , Nowakowska Sylwia K. , Waeckerlin Aneliia , Mousavi Fatemeh S. , Popova Olha , Decurtins Silvio , Stoehr Meike , Waeckerlin Christian , Hill Jonathan P. , Shah Zaman Sameena , Liu Shi Xia 
Published: September 2023

By their role in biochemistry, porphyrins have played a central role for “Chemistry beyond the molecule”, long before the term ‘supramolecular chemistry’ has been coined. It is interesting that the bio-chemical functions of porphyrins predominantly derive from the center metal atom, its coordination shell and the coordination-site specific properties. The integration of porphyrins into bio-molecules is safeguarded by covalent chemistry and not ‘supra-molecular’ as such. Nevertheless, square planar porphyrins and pthalocyanines take a decisive role in the development of on-surface supra molecular chemistry: This for their excellent stability and for the many ways they can be functionalized with ligands. Thereby, porphyrin and phthalocyanine chemistry paved the way towards the systematic investigation of many different functional groups known to direct self-assembly and their influence on the formation of on-surface supramolecular layers and chains. I will review the results of on-surface supramolecular assembly experiments performed at the solid-vacuum interface with CN-[1], CN-phenyl, alkoxy [1], fluoro [2] and fluorophenyl [3] and di-methylene-aniline derived functional groups and discuss the supramolecular ordering in terms of estimated binding energies and formation kinetics. It is also interesting to compare the supramolecular ordering in fluids with the constrained ordering of molecules confined to surface substrates. Further insight into the directing power of the individual functional groups derives from a fresh look at the three-fold symmetric pyramidal sub-Phthalocyanines.
Fig. 1) Supramolecular ordering of substituted porphyrins in networks fromed by CN-phenyl interaction: a) and b) show higher magnification micrographs of c) and d) in two different imaging modes emphasizing the pi orbitals (HOMO) and the alkyl substituants, respectively. e) shows the dynamicity of a network from sterically more demanding alkyl-phenyl substituents. (for further details see [1] and references therein)
[1] N. Wintjes et al. J. Am. Chem. Soc. 2010, 132, 7306–7311
[2] J. Girovsky et al. Nature Communications 2017 8:15388
[3] S. Nowakowska et al. ACS Nano 2018, 12, 768−778.

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Carbon Nanotube Based Broadband Solar Thermal Absorber Coatings
Authors: Wang Dan , Hall Timothy , Snyder Stephen , Inman Maria , Taylor E. Jennings 
Published: September 2023

Radiant energy conversion and storage eliminate the mass transfer process induced power output limitation, and open a new vista for energy utilization. An effective system for harvesting radiant energy from both solar and thermal radiation will be beneficial for further radiant energy utilization. On the other hand, space observatory missions require low-reflectivity surfaces/coatings for space-borne instruments, such as seeker telescopes, optical sensors, etc., to minimize stray and reflected light on targeted telescope and baffle materials and construction. The excellent optical, thermal, and mechanical properties of carbon nanotubes (CNTs) make them as ideal coating materials for absorbing the broadband spectrum across UV-Vis-IR regions.
In this presentation, Faraday Technology will discuss an innovative electrophoretic deposition (EPD) manufacturing process, based on the use of pulsed electric fields, for controlled, reproducible, scalable deposition of a wide variety of carbon nanotube based coatings across a broad range of substrates, geometries and sizes (Figure 1 a). The effects of waveforms, electrolytes, substrates, etc. on the formation of robust and uniform coating will be discussed in this talk. The optical properties, and environmental survivability of carbon nanotube coatings will be demonstrated via a variety of testing or characterizations. The CNT coatings show the total hemispherical reflection of 0.5% - 1% across UV-Vis to near infrared (NIR) wavebands, which is much lower than the reflectance of the typically used Z306 black paint (Figure 1 b). These CNT coatings also withstood simulated launch conditions vibrational tests, and demonstrated no weight loss and optical degradation. Furthermore, the CNT coatings were evaluated for atomic oxygen erosion resistance in a simulated low earth orbit (LEO) environment, and showed enhanced resilience when compared to Kapton and HOPG. Faraday will also introduce their applications in low-reflective coatings and solar thermal absorbers for radiant energy harvesting and conversion.
In summary, a scalable EPD manufacturing process for fabricating carbon nanotube based coatings have been developed at Faraday for the applications in the field of low-reflective coatings and broadband solar thermal absorbers.
Acknowledgements: The financial support from NASA SBIR program through contracts No. 80NNSC18P2062 & 80NSSC19C0177, DARPA SBIR program through grant No. W31P4Q-22-C-0014, DOD MDA STTR program through grant No. HQ0147-19-C-7065, and DOD Air Force SBIR program through grant No. FA9550-22-P-0015 are acknowledged.

Figure 1
Influence of Crack Tip Plasticity on the Microstructure and Corrosion Behavior of CA6NM Stainless Steel Measured Using Scanning Electrochemical Cell Microscopy (SECCM)
Authors: Yassine Sarah , Lacasse Robert , Deschênes Pierre-Antony , Brochu Myriam , Mauzeroll Janine 
Published: September 2023

The existence of cracks within ductile materials such as stainless steel induces local plasticity around the crack tip that may cause local changes in the microstructure. Although the plastic deformation and microstructural heterogeneities are expected to influence the electrochemistry of the area around the crack tip, few are the studies that correlate the factors- strain and corrosion- together.
In this work, we analyze the corrosion behavior of pre-cracked CA6NM compact tension stainless steel samples taking into consideration the variations in the microstructure resulting from the local plasticity at the tip of a crack. Multiple surface microstructure analysis are obtained to characterize the surface properties of the plastic zone. The localized corrosion behavior around the crack tip is studied using the scanning electrochemical cell microscopy (SECCM) technique. The acquired micro open circuit potential (OCP) and micro potentiodynamic polarization (PDP) curves were used to generate corrosion potential and corrosion current maps of the scanned area. The electrochemical behavior of the crack tip was compared with that in the un-deformed area of the same sample.
The ability to conduct direct electrochemical measurements at microscopic scale through SECCM allows to correlate the localized corrosion behavior to the microstructure analysis obtained before. This work paves the avenue to studying the synergistic effect of fatigue damage on the local corrosion behavior through monitoring both simultaneously.
High Entropy Oxides Synthesis by Rapid Plasma Generation with Applications Towards Electrocatalytic Hydrogen Generation
Authors: Abdelhafiz Ali , Li Ju 
Published: September 2023

It has been challenging over the past three decades to find viable energy alternatives with higher efficiency and lower cost to beat the non-friendly and commercially dominant hydrocarbon energy sources. Hydrogen is deemed to be one of the most prominent candidates, as a green fuel. Hydrogen can be generated in abundance from water splitting. Utilization of hydrogen in fuel cells, with no doubt, produces no harmful gases. Nevertheless, the two parts of the technology: hydrogen production and reduction are cumbersome. Both processes rely on kinetically sluggish electrocatalytic reactions. Enormous research efforts have been spent, with thousands of studies presented in literature, despite the technology left with a dim light shed on from commercial and practical point of views. Many materials-related challenges are hindering the flourishing of green hydrogen technology, where poor catalyst durability is a major challenge, despite being made from very expensive elements (e.g., Ir, ru or Pt). Therefore, gigantic effort of research has been devoted to find inexpensive alternatives. Transition metals showed interesting performance towards water splitting (e.g., oxygen evolution (OER)).
Recent research showed that electrocatalysts designed by alloying two or more elements (e.g., transition metals) showed promising enhancement in catalytic activity and durability due to synergistic effects from alloying, such as strain engineering or electron exchange. The potential of the alloying approach is constrained by standard synthesis methods (e.g., wet chemistry and thermal decomposition techniques) due to the governing thermodynamics rules (e.g., miscibility of the different alloying elements). That renders the synthesis of high entropy alloys (HEA), with more than 3 elements, to be complicated and tedious to achieve by those conventional methods.
In the presented talk we are presenting the utilization of microwaves to generate plasma to synthesize metastable high entropy oxides (HEA) and their outstanding catalytic performance towards OER, in correlation to their unique chemistries and structures. Plasma generated enable temperature increase of the precursor substrate to elevated levels (~1000s °C), in conjunction with rapid cooling, within seconds range. Our results show successful synthesis of non-noble metals HEA NPs, possessing higher catalytic activity than IrO2 catalyst for OER. The nature of the alloying elements dictates OER activity by promoting different oxidation states of the catalytically active transition metals (e.g., Fe, Ni and Co). Our developed techniques resulted in formation of super-strong metal-carbide bonds “chemically welding” HEA NP to the catalyst support.
Exsolution Synthesis of Alloyed Nanoparticles from Perovskite Oxide by Plasma
Authors: Li Qinghao , Zhou Jun , Zhu Zi-He , Fu Lei , Yang Jiaming , Wu Kai 
Published: September 2023

Bimetallic alloy nanoparticles (NPs) exsolved on the surface of perovskite oxides (ABO3) alter the structural and electronic properties of the primarily monometallic counterparts. These synergistic effects make the whole material present superior electrolytic and catalytic performances. The strong bonding interaction between alloy NPs and perovskite substrate enables the stability and durability of the catalysis.
However, traditional thermal exsolution requires a long-time treatment at a high temperature. Researchers have been pursuing more time-saving and energy-efficient alternative routes. Herein, a low-temperature and fast pathway based on the dielectric barrier discharge (DBD) reactor is provided to in-situ exsolve alloy NPs. A favorable activity of the catalyst for CO oxidation is demonstrated. Additionally, we conclude that the factor restricts metallic agglomeration is the morphology of the substrate. Even after an overtime plasma treatment, the exsolved alloy NPs are still embedded in the porous structure of perovskite oxides.
(Invited) Efficient Carbon Sulfonation Using Plasma in Contact with Dilute Sulfuric Acid
Authors: Takeuchi Nozomi , Deng Siqi , Takahashi Katsuyuki , Tachibana Kosuke , Hieda Junko , Li Oi Lun 
Published: September 2023

Heterogeneous catalysis is a promising technology in biomass valorization because of its high reactivity, easy post-separation, and great recyclability compared to homogeneous catalysis. Various functionalized catalytic materials have emerged as promising alternatives to the homogeneous liquid acid catalyst, such as carbon materials, metal–organic frameworks, and metal nanoparticles. Among them, carbon materials such as carbon nanotube, graphene oxide, carbon black, and so on have been investigated as catalysts for cellulose hydrolysis to produce glucose.
Carbon materials show considerable catalytic activity by functionalization with active acidic groups including hydroxyl groups (-OH), carboxyl groups (-COOH), and sulfonic groups (-SO3H). Hydroxyl and carboxyl groups on the carbon catalysts act as connection center to access cellulose, where sulfonic group serves as the active site to cut off the linkage between glucose units in cellulose. So, the surface modification of carbon materials with these functional groups, namely, carbon sulfonation process, becomes the determining step to producing efficient carbon acid catalysts. Conventional methods for the carbon sulfonation are the hydrothermal and reflux method, in which hazardous chemicals are necessary, such as concentrated sulfuric acid (95–98%), chlorosulfonic acid, fuming sulfuric acid, or 4-benzenediazoniumsulfonate under elevated temperature for dozens of hours. As a green and effective carbon sulfonation process, we have utilized gas–liquid interfacial plasma (GLIP).
In the GLIP process, plasma is generated between the tips of multi-needles and the surface of dilute sulfuric acid which contains carbon particles in N2/Ar gas mixture. The optimized catalyst synthesized from graphene nanoplatelets by the GLIP process achieved a conversion rate of 41.5% with high glucose selectivity of 84.3%, which is superior to performance of catalysts synthesized by the hydrothermal method. The concentration of sulfuric acid, reaction temperature, and reaction time for the GLIP process were 1 M, 40℃, and 0.75 h, respectively while those of the hydrothermal method were 18 M, 200℃, and 24 h, respectively. Thus, the GLIP process is less hazardous and more efficient. Significantly, the catalyst synthesized by the GLIP process also exhibited superior recyclability of 95.9% in 3 times cycle tests for cellulose hydrolysis.
Recently, we have investigated the mechanism of carbon sulfonation in GLIP processes. Active species produced near the gas–liquid interface such as ·OH, SO3, and HOSO2· probably play important roles in carbon sulfonation. We are trying to observe gas-phase active species by Fourier transform infrared spectroscopy and quadrupole mass spectrometer, and liquid-phase active species by electron spin resonance spectroscopy.
(Digital Presentation) Electrochemical Reduction of Pressed Tungsten (VI) Oxide on a Solid Electrode in a Melt of Calcium and Sodium Chlorides
Authors: Medvezhynska Olha , Omel'chuk Anatoliy 
Published: September 2023

This report presents the results of research on the electrochemical reduction of tungsten (VI) oxide in a molten electrolytic mixture of CaCl2-NaCl of eutectic composition. The electrochemical behavior of tableted WO3 on a solid tungsten electrode was studied by voltammetry. Analysis of the obtained products was carried out by X-Ray diffraction and electron microscopy.
During the electrochemical reduction, pressed cylindrical samples were placed on a tungsten disk, which served as a cathode. A silica cloth impregnated with a CaCl2-NaCl eutectic melt was placed on top of the tableted sample in order to prevent a short circuit in the cell. The silica cloth and tableted tungsten oxide were pressed to the cathode by the anode. The anode was made of low-porous graphite, and the current was supplied to it with a molybdenum wire. The electrode assembly prepared in this way was placed in a crucible with molten chlorides of calcium and sodium.
Analysis of the obtained results indicates that reduction processes occur in pressed tungsten oxide (Fig. 1, a). According to the results of X-Ray phase analysis, in the surface layer of pressed tungsten (VI) oxide, which was in contact with the cathode, when the amount of electricity (Q) twice greater than that required for the complete recovery of loaded tungsten trioxide was passed, the following phases were detected: W, CaWO4 and a small amount of NaxWO3. Having studied the entire volume of the tableted sample, the following phases were recorded: NaxWO3 (main phase) and CaWO4, W (Fig. 1, b). The formation of phases of sodium and calcium tungstates is explained by the interaction of tungsten trioxide with the components of the melt. Passing electricity through the pressed sample causes electrochemical reactions to occur with the formation of tungsten metal, which grows from the cathode/WO3/electrolyte interface into the sample volume.
During galvanostatic electrolysis (i=0.4 A/cm2) of a pressed sample of tungsten (VI) oxide with a mass of 0.43 g (r=0.4 cm, h=0.174 cm) and a duration of 6 hours (Qpractical/Qtheoretical = 6), the degree of extraction of tungsten from tungsten trioxide is not less than 97.48%, and the current yield is about 29.06%. The X-Ray diffraction pattern of the obtained product under such conditions confirms the presence of only a monophase of crystalline tungsten (Fig. 1, b).

Figure 1
Rhenium Electrodeposition to Enable Functionally Graded Films
Authors: McBride Michael , Clark Courtney L , Hooks Daniel E , Dervishi Enkeleda 
Published: September 2023

Rhenium (Re) has one of the highest melting points of all the metals with a high modulus of elasticity and superior tensile strength when compared to other refractory metals. However, processing challenges from the high temperature stability combined with the relative occurrence require advanced manufacturing approaches to leverage the unique properties of rhenium. The electrodeposition of rhenium has received renewed attention in the past decade as a scalable approach to apply uniform coatings to enable a wide range of applications in aerospace, nuclear, catalysis, biomedical fields. However, Re has traditionally been difficult to deposit by electrolysis from aqueous solutions due to the over potential for hydrogen evolution and complex electrochemical reactions.
Beginning with the perrhenate anion (ReO4
-), reduction from the +7 oxidation state must occur to deposit metallic Re. The exact mechanism of this process is still unknown with reductions to ReO2, ReO3, and Re2O5 along with metallic Re. Combined with the hydrogen evolution reaction, Re coatings are generally deposited at low faradaic efficiency, are brittle, and limited in the obtainable thickness (sub-micron).
Herein, we present systematic studies progressing towards the development of stable and efficient electrolytes to enable the electrodeposition of thick (100+ microns) Re coatings. Borrowing the water-in-salt electrolyte method from the lithium battery literature enables near room-temperature electrodeposition of Re. Specifically, we correlate nucleation and growth mechanisms of Re with the ability produce thick coatings. Pulse/pulse reverse electroplating was applied to manipulate the obtained grain structure and distribution of rhenium moieties. Correlations between the electrolyte composition and the pulse parameters with the observed morphology will be discussed with an emphasis on enabling industrially relevant electroplating processes.
The goal of this project is the electrodeposition of rhenium-cobalt (Re-Co) graded compositional/density samples of millimeter thickness. Thus, understanding how to transition from a coating or pure metallic rhenium to a graded composition of Re-Co as a function of dynamic processing conditions will be presented.
EIS Measurements to Quantify the Content of Organic Additives in Complex Matrices of Copper Plating Baths
Authors: Verrucchi Margherita , Comparini Andrea , Bonechi Marco , Mariani Elena , Meoli Arianna , Donati Lorenzo , Innocenti Massimo , Giurlani Walter 
Published: September 2023

Commercial plating baths may contain a large number of organic additives that play an important role in ensuring good-quality deposits. During electrodeposition process these compounds tend to wear out and degrade, so they must be frequently monitored and dosed to keep constant their concentration. Plating baths are complex matrices in which organic additives are present in minimal quantities compared to the other components, electrochemical methods, therefore, represent a reliable alternative to conventional chromatographic techniques because they allow quantitative analyses to be carried out considering the effects of additives on the electrodeposition rate regardless of their chemical composition and provide, at the same time, useful information about the condition of the bath. Methods based on the Cyclic Voltammetric Stripping (CVS) technique can be employed to quantify additives generally used in commercial acid copper plating baths. However, such procedures tend to be time and reagents-consuming and do not always provide accurate results. Electrochemical Impedance Spectroscopy (EIS) can represent a reliable alternative because it allows to achieve a detailed knowledge of the function of each additive and the interactions between them and to study the aging of plating baths [1]. EIS measurements were performed to quantify the three main additives present in commercial acid copper plating baths. These baths are widespread in different industrial sectors, such as fashion and electronic. The experiments were performed in three-electrodes cell, at 30 °C, by using a 105 – 10-2 Hz frequency range. A large number of samples were investigated for a statistical treatment of the results that allowed us to find correlations between the concentration of each additive and some of the components of the equivalent circuit used to fit the data. The procedure applied to real samples provided promising results.
The authors acknowledge MUR and EU-FSE for financial support of the PhD fellowship PON Research and Innovation 2014-2020 (D.M 1061/2021) XXXVII Cycle in Chemical Sciences.
References
[1] Gabrielli, C. et al. Journal of Applied Electrochemistry 2008, 38, 457-468, doi: 10.1007/s10800-007-9459-1
Integrating Sustainable Design into Advanced Electrochemical Manufacturing
Authors: Bruce David Robert 
Published: September 2023

Considering the green engineering principles developed by Anastas and Zimmerman or detailed from the Sandestin conference of 2004 as presented by Abraham and Nguyen there is a duty of care as environmental stewards of our technology to closely examine where we can reduce impact regarding nascent electrochemical technologies.
Comparison of state-of-the-art electrochemical manufacturing technologies highlight the design options competing technologies offer when we consider the sourcing, manufacturing, emissions, and other ways of embodying the environmental footprint of our designed processes.
Impact on natural systems, circular life-cycle thinking and creating engineering solutions beyond our current or dominant manufacturing technologies to improve, innovate and invent solutions for a transition to a clean energy future are highlighted. Principles of conservation and improvement of natural ecosystems are considered to inform novice scientists and engineers and lead to insight in opportunities for advanced system developments for mature industry representatives and experienced experts.
Challenges in greening of existing systems offers opportunities for continued growth in the industrial domain. Triple bottom line examination of how our actions can improve manufacturing processes, as well as benefit globally relevant sustainable development goals. Reframing the basis for how we design electrochemical processes from a cost-efficiency relationship to include additional considerations in our practice using simple guidelines to address cell architectures, integration and interconnection of energy and material flows, and careful material selection are shown to have a win-win benefit when we examine intergenerational scope of our practice.