bluuebunny/crossref_metadata_2025 huggingface dataset:
Microstructure and the Plating/Stripping Behavior of Magnesium Metal Negative Electrode for Rechargeable Magnesium Batteries
Authors: Chang Yung-Jen , Huang Yu-Shan , Chu Peng-Wei
Published: September 2023

Recently, rechargeable magnesium (Mg) battery systems attract lots of attention owing to their promising theoretical energy density, low cost from the natural abundance of Mg, and less dendritic growth of Mg during charging. Nevertheless, rechargeable Mg battery systems suffer from sluggish reaction kinetics on the electrodes and poor cycle life, which greatly limit their practical competitiveness. Most studies focus on the development of novel electrolytes and their feasibility for rechargeable Mg batteries, while the plating/stripping behavior of Mg metal negative electrode during the charge/discharge cycle is relatively less studied.

Therefore, in this research, the platting/stripping behavior of the Mg metal electrode and the resultant surface microstructure after cycling were investigated in an all phenyl complex (APC) (PhMgCl + AlCl3 in THF) electrolyte. A Swagelok-type Mg||Mg symmetric cell was used in this study with an air-free transfer system to prevent the charged/discharged electrode from oxidation when moving to a scanning electron microscope (SEM) to observe the surface microstructure.

When discharging the pristine pure Mg electrode, the stripping was found to be highly localized with numerous discharge holes on the electrode surface. Interestingly, in the subsequent charging stage, the platted Mg preferentially deposited along the circumferences of the discharge holes, which might be related to the distribution of Mg species right after discharge and the surface conditions of the discharged surface. Later discharge was found to preferentially strip the platted Mg and leave marks around the discharge holes. In addition to cycling on a pure Mg electrode, the platting/stripping behavior and the resultant microstructure of Mg metal deposited on a copper (Cu) current collector were also studied and will be discussed for potential anode-free Mg battery applications. Regardless of the platting/stripping conditions, no dendritic Mg was found during the charge/discharge cycles.

Figure 1
High-Ni NMC Cathode Material with Concentration Gradients in Lithium-Ion Batteries
Authors: Shang Mingwei , Niu Junjie
Published: September 2023

Due to the high capacity and the high discharge potential, Ni-rich layered cathode materials are considered as a class of promising cathode material and attracting considerable attention. Because of the Li+/Ni2+ cation mixing, Li residues, overcharging, crystal orientation of the secondary particles, poor cycling stability and rate capability are usually received in lithium ion batteries. In this presentation, we introduce a layered NMC811 with Ni-gradients by using metal-organic framework (MOF) as precursor (
Cell Reports Physical Science
, 3 (2022), 100767). The self-healing phase by forming a cation mixing layer on the surface of particles effectively improved the structural stability by suppressing the phase transition and internal cracks upon cycling. In the half-cell battery, an initial capacity of 203.5 mAh/g at 0.1 C and a capacity retention of 88.5% after 300 cycles at 1/3 C were obtained. The battery still showed a CE of 99.47% at 1/3 C after 300 cycles at 55 ℃. In addition, the full-cell battery showed a capacity retention of >86.7% with a CE of >99.86% at 1/3 C after 300 cycles. Moreover, a pouch cell delivered an initial capacity of 297.62 mAh and a CE of 99.48%, which contributed to an energy density of 216.41 Wh/kg. The capacity retention was still as high as 84.1% after 500 cycles at 1.0 C.

Keywords: Li-ion batteries; Ni-rich cathode materials; MOF; Concentration gradient
Al-Fe Based Molten Salts for Long Duration Energy Storage
Authors: Maraschky Adam M. , Small Leo J. , Spoerke Erik D. , Percival Stephen J.
Published: September 2023

There is a need for high energy density long duration energy storage that utilizes earth abundant elements, such as Al and Fe. Energy storage devices that utilize molten salt electrolytes can take advantage of these earth abundant materials and promise to deliver high energy densities. Continued development and in-depth investigation of these fully inorganic, molten salt electrolytes is necessary for the continued progress of low-cost battery technologies. We have been exploring the properties of a new molten salt system which utilizes Al and Fe components and can feasibly be operated as an electrochemically active medium for long duration energy storage. Ternary molten salt compositions of AlCl3-FeCl3-NaCl and AlCl3-FeCl2-NaCl were evaluated for their phase behavior and electrochemical performance at intermediate temperatures (~160 - 210 °C). We found that certain compositions of AlCl3-FeCl3-NaCl were fully or nearly fully molten at 160 °C and that more AlCl3 was needed in the melt to facilitate the FeCl2 dissolution. The electrochemistry of these salts was probed and found that the Fe species will cycle between the Fe3+/Fe2+ oxidation states (as FeCl3/FeCl2) but that at lower temperatures, the FeCl2 will precipitate out of the melt and block the electrode. By increasing the test temperatures, the produced FeCl2 dissolves into the melt allowing the un-blocked electrode to sustain large reduction currents. Future work will investigate ways to increase FeCl2 concentration in the melt and to facilitate its oxidation in order to optimize the molten salt catholyte electrochemical behavior and demonstrate it in a working battery.

This work was supported by the U.S. Department of Energy’s Office of Electricity through the Energy Storage Research Program, managed by Dr. Imre Gyuk. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC, a wholly-owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy or the United States Government.

SAND2022-16623 A
Investigation of Suitability of Electrolytes in a Trivalent System
Authors: Gates Leslie , Sa Niya
Published: September 2023

As lithium-ion batteries (LIB) start to approach their theoretical limit, researchers are focusing on alternatives such as nonaqueous multivalent systems. There are many advantages of multivalent systems such as higher natural abundance, low cost and possible high volumetric capacity. Suitable electrolytes are vital for the development of such multivalent battery systems which offer compatibility of utilizing metal anode. To create a better understanding of the opportunities and challenges of the trivalent electrolytes in aluminum batteries, this work investigates the reaction mechanisms and SEI interactions at the electrolyte/electrode interface.
Improving Cycling Performance of Anode-Free Lithium Batteries by Pressure Control
Authors: Lim Hyung-Seok , Cao Xia , Zhang Ji-Guang
Published: September 2023

For the anode-free Lithium (Li) batteries (AFLBs), an uniform/dense Li deposition is ideal to stabilize the interface with a solid electrolyte interface (SEI) layer between copper current collector and liquid electrolyte, and minimize the electrolyte/lithium consumption for long-term cell operation. Unlike in the case of Li-ion or Li-metal battery systems where Li metal foil and graphite anode can serve as a cushion to uniformly distribute the pressure, the deposited Li in AFLB is much more sensitive to the pressures and current distribution applied on the copper foil electrode in the AFLBs. We found that the commercial coin cell components lead to a non-uniform/porous Li deposition and further a brittle SEI layer after the cell was charged to 4.5V and discharged to 3.5V, respectively. This non-uniform interface results in poor cycling performance of AFLB coin cells. In this work, we optimized the internal pressure in the coin cells and revealed the internal pressure effect on stabilizing a SEI layer and improving AFB cycling performance.
Uncertainty Weighted Distribution of Relaxation Time Analysis of Battery Impedance Spectra Using Gaussian Process Regression for Noise Estimation
Authors: Bartsch Christian Hippolyt , Jin Limei , Bereck Franz Philipp , Mertens Andreas , Eichel Rudiger-A , Scheurer Christoph , Granwehr Josef
Published: September 2023

A common technique for characterizing electrochemical systems is the combination of electrochemical impedance spectroscopy (EIS) and equivalent circuit modeling (ECM). However, choosing a suitable electrical circuit usually requires a-priori knowledge of the investigated system. By combining ECM with a distribution of relaxation times (DRT) analysis, relevant features found in the impedance data can be distinguished more clearly and, ideally, their number can be determined.

Since the data acquired by EIS shows heteroscedastic noise behavior, using uniform weighting in the DRT can result in either under- or overregularization of certain parts of the data. This can lead to a significant misinterpretation of the system. To account for that, the frequency-dependent noise is estimated with statistical noise characterization by obtaining multiple EIS spectra of a commercial Lithium-ion coin cell at the same SOC. Since repeating a multitude of measurements in a real-life application is often impractical due to time constraints, Gaussian process regression (GPR) using only a single data set is introduced as an additional method for noise estimation.

It is shown that incorporating noise-weighted DRT analysis into ECM parameterization facilitates the choice of suitable equivalent circuits and can yield a more robust parameterization of the investigated system. Additionally, the use of GPR for noise estimation can supply sufficiently accurate results with the use of minimal input data.

Figure 1
Indium Alloy as Anodes for Rechargeable Calcium Ion Batteries at Room Temperature
Authors: Briselli Vincent , Sa Niya , Yang Zicheng , Cora Saida
Published: September 2023

Rechargeable multivalent ion batteries are poised to deliver the necessary breakthroughs in energy density and stability required for extended-range electric vehicles and large-scale grid energy storage. Calcium ion batteries are of interest owing to their high theoretical energy densities, natural abundance, and safety, yet are hindered by calcium’s strong interactions with non-aqueous electrolyte solutions and a general lack of suitable intercalation hosts. In order to realize the high voltage and theoretical capacity of a calcium-ion battery, replacement of the Ca metal anode with new electrode materials that can operate reversibly in conventional electrolyte systems is necessary, beginning with fundamental studies to identify novel intercalation or alloy-type hosts which can provide high-Ca content while avoiding considerable volume expansion and capacity loss. In this work, research into a novel indium anode as a host for Ca2+ ions in conventional electrolytes at room temperature is presented.
Color-Switchable Hydroxide Double-Layer Films for Electrochromic Energy Storage Devices
Authors: Lee Young Hoon , Sung Yung-Eun
Published: September 2023

Electrochromic devices have received great attention because of the increment in electrochromic smart window markets for building and vehicles. Recently, electrochromic materials not only enhanced electrochromic performances but also provided additional functions (energy storage, light-emitting diodes, and solar cell). Meanwhile, electrochromic devices are being developed with the goal of large-scale applications such as electrochromic smart windows for building and vehicles, there are still significant needs for reliability of materials and simplify their fabricating processes. In this study, double-layer hydroxide films are reported as energy-storable electrochromic materials with ultrafast kinetics in alkaline electrolyte. Core/shell-like cobalt hydroxide/nickel hydroxide nanofilms deposited within short electrodeposition time have capabilities for multiple color changes (yellow-green-brown) and show extremely fast colored/bleached switching time that are comparable to state-of-the-arts. Furthermore, the cobalt hydroxide/nickel hydroxide nanofilms were indicated high capacitance and rate performance as a battery-type supercapacitors, with higher electrochromic kinetics than those with similar level of capacities for energy storage.
Nonaqueous Magnesium Electrolyte Intermediates and Kinetics
Authors: Asselin Genevieve , Yang Zicheng , Sa Niya
Published: September 2023

Nonaqueous Magnesium Ion batteries are a promising strategy to overcome the shortcomings of Li ion batteries given magnesium’s lowered abundance, cost, environmental impact and increased energy density and charge-carrying capabilities. Multivalent systems are challenging to study and a mechanistic understanding of how these types of electrolytes function is hazy at best. Where studies have attempted to better characterize the mechanism of charge transfer, details of electron movement are not explicitly reported.Chemical steps are often reported to precede electron transfer steps as well, but the exact nature of these chemical steps have not been proven or well described yet either. The studies herein hope to bridge some of these gaps in knowledge for magnesium electrolyte systems with studies of kinetics and intermediate formation. The highly contested Mg+ intermediate was observed to form during electrodeposition of Mg for all, and during dissolution in some of the studied electrolytes which included three non-halogenated Mg(TFSI)2electrolytes in various organic solvents and a more traditional halogen-based Grignard APC electrolyte.
Non-Nucleophilic Electrolytes with Non-Fluorinated Hybrid Solvents for Long-Life Magnesium Metal Batteries
Authors: Sun Yue , Lu Yi-Chun
Published: September 2023

Growing energy demands and the widespread of renewable power sources call for high-energy storage systems beyond lithium-ion batteries (LIBs). Rechargeable magnesium batteries (RMBs) are high-energy, safer, and more cost-effective alternatives to LIBs and lithium metal batteries (LMBs) thanks to Mg’s high volumetric capacity (3832 mAh cm-3)1, low theoretical potential (-2.37 V vs SHE)2 and earth-abundance3. Non-nucleophilic and non-fluorinated compounds are the most important class of materials to enable sustainable rechargeable magnesium (Mg) batteries, however, they suffer from poor stability due to the formation of unstable solid-electrolyte-interphase (SEI).4 Here, we design a hybrid-solvent electrolyte by dispersing a non-nucleophilic solution in a non-fluorinated weakly-coordinating solvent to prevent parasitic reactions and form stable SEI. This strategy significantly improved the cycle life of the Mg anode from 24 to 4000 hours (in Mg-Mg symmetric cells) and realized a stable cycle life of Mg-Mo6S8 full cells for more than 2300 hours with an average CE of 99.96%. The non-fluorinated weakly-coordinating solvent suppressed uneven Mg growth and contributed to the formation of polymeric SEI, which filled the cracks of pristine SEI, preventing side reactions and passivation. This strategy revealed the critical role of weakly-coordinating solvents in stabilizing Mg anode for reversible Mg batteries.

References:

[1] H. S. Kim, T. S. Arthur, G. D. Allred, J. Zajicek, J. G. Newman, A. E. Rodnyansky, A. G. Oliver, W. C. Boggess, J. Muldoon, Nat. Commun., 2 (2011) 427-433.

[2] R. Attias, M. Salama, B. Hirsch, Y. Goffer, D. Aurbach, Joule, 3 (2019) 27–52.

[3] W. Guo, S. Chen, N. Hussain, Y. Cong, Z. Liang, K. Chen, Plant Signal. Behav., 10 (2015) e992287.

[4] Z. Lu, A. Schechter, M. Moshkovich, D. Aurbach, J. Electroanal. Chem., 466 (1999) 203–217.

Acknowledgments:

This work is supported by a grant from the Innovation and Technology Commission of the Hong Kong Special Administrative Region, China (Project No. ITS/219/21FP).
Advancements in Fundamental Understanding of Li+ Solvation and Transport in Liquid Electrolytes
Authors: Leverick Graham , Shao-Horn Yang
Published: September 2023

In this talk, we summarize a number of recent works where we provide new insights into the solvation and transport of Li+ ions in liquids electrolytes. Through the study of ionic Seebeck coefficients, we show how the temperature-dependence of Li+ solvation differs in high and low dielectric constant solvents. We show that in the high dielectric constant DMSO, ionic Seebeck coefficients are dominated by changes in the configurational entropy of the bulk electrolyte, where as in low dielectric constant DME, changes are dominated by the temperature- and composition-dependent electrolyte permittivity which influences the enthalpy of solvation. In another work, we examine how the energy landscape changes the transport mechanism on Li+ ions. We show that decreasing instantaneous shear modulus and increasing solvent DN lead to a vehicular ion transport mechanism. However, in solvents like EC, more facile solvent exchange in the Li+ solvation shell can enable a solvent exchange mechanism, and shortening the Li+ hopping distance can further facilitate Li+ hopping in some electrolytes. We conclude by discussing how these new, fundamental understandings can inform rational design of next-generation electrolytes with enhanced properties like ionic conductivity and Li+ transference number.
The Application of Permanent Magnets for High Capacitance Polyaniline-Modified Electrodes
Authors: McLeod William T , Sheelam Anjaiah , Kroiss Aspen , Bell Jeffrey Gordon
Published: September 2023

Supercapacitors are energy storage devices useful for their rapid charging and discharging but held back by poor energy density. Electrode conductivity and surface area are often increased to improve the energy storage of supercapacitors. Polyaniline (PANI) is an electroactive polymer used in supercapacitors for its high conductivity and ease of electrochemical deposition. It has also been shown that the application of a constant magnetic field can alter both the morphology of electrodeposited polymers and the rates of radical-based reactions. Additionally, the application of a strong magnetic field over a net movement of ions, such as is induced by an electric field or concentration gradient, induces rotational convection via the Lorentz force. In this work, we used a permanent magnet as a zero-energy-input method to influence the deposition of PANI for high capacitance electrodes with improved energy storage. The polymer was deposited onto glassy carbon or platinum electrodes using cyclic voltametric, potentiostatic, and pulsed potential techniques, and the capacitance of the fabricated electrodes was measured by cyclic voltammetry. With an optimized method, the application of a magnetic field increased the electrodes’ capacitance by more than 50% over the control. This presents a method for the fabrication of higher energy density supercapacitors with no additional energy input.
Isolating Overpotential Contributions in Redox Flow Batteries Using a Membrane-Based Reference Electrode
Authors: Bachman Ridge M. , Cross Nicholas R. , Pate Callaway , Owuor Peter , Khan Abdullah , Hall Derek M.
Published: September 2023

Redox flow batteries (RFBs) are a promising solution to the increasing demand for energy storage as a transition from carbon-intensive to renewable energy sources continues. However, many flow battery chemistries still have low energy efficiencies due to their poorly understood overpotential contributions. To minimize RFB inefficiencies, many studies have explored oxidative treatment methods of their carbon-based electrodes which have provided conflicting results. Though three-electrode measurements are often the best method of isolating overpotential contributions, challenges associated with inserting a reference electrode into a typical laboratory flow battery design have limited most full cell studies to two-electrode measurements. Here, we demonstrate how a low-profile membrane-based reference electrode can be readily incorporated into standard laboratory full cell test systems. The reference electrode provides the ability to measure the potential of each electrode, providing new possibilities with full cell testing. This new membrane-based approach was used to examine overpotential contributions of a vanadium redox flow battery (VRFB) and a thermally regenerative flow battery (TRB). For the VRFB system, the negative electrode overpotential was consistently the largest contributor to cell overpotential. With untreated electrodes, the negative electrode added 227 mV of overpotential to the cell which was 95% of the total cell overpotential. After oxidative treatments, the negative electrode contribution decreased to 155 mV for the same setup. For the TRB system, the negative electrode was also the largest source of overpotential after ohmic contributions.
Forward Bias Polarization of Bipolar Membranes Is Controlled by Acid-Base Equilibria and Electrolyte Exchange Rates
Authors: Lun Toh Wei , Dinh Hieu , Chu An , Surendranath Yogesh
Published: September 2023

Bipolar membranes (BPMs) are an emerging technology supporting a myriad of electrochemical applications. BPMs are increasingly gaining interest for forward bias applications, such as to increase cell voltage or perform product recovery. However, the factors that control forward bias polarization in the presence of complex electrolyte mixtures remain poorly understood. Herein, we demonstrate that the development of an interfacial pH gradient strongly impacts the forward bias polarization curve for a BPM containing mixtures of electrolytes with different acidities/basicities. The thermochemical and transport properties of these electrolytes influence regions of current takeoff and limiting current. We construct a model of site competition that explains the observed current-voltage behavior. These findings have significant implications for the design of energy-efficient, next-generation forward bias BPM devices.
Hydrogen Exchange and Diffusion Kinetics at Elevated Temperatures in Proton-Conducting Solid Oxide Materials
Authors: Yatoo Mudasir A , Skinner Stephen J
Published: September 2023

Storage of purified hydrogen is one of the central challenges in addressing climate change and reducing our reliance on fossil fuels for energy conversion and storage, and therefore there is a global surge in research and development concerning hydrogen purification and storage. In this regard, we are studying proton conduction in solid oxide materials at elevated temperatures for applications in hydrogen separation and compression membranes. Hydrogen compression is the most recommended method to store hydrogen for automotive applications as it allows an increase in the hydrogen volumetric energy density.

Traditionally the protonic conductivity in these materials is measured by indirect methods. For example, conductivity measurements in mixed gas atmospheres, comparing for example dry N2 with humidified N2, thereby allowing the contribution of protons to be evaluated. In this study, we for the first time report the evaluation of protonic conductivity in BaZr1-xCexY0.2O3−δ, BaZr0.1Ce0.7Y0.2–xYbxO3–δ and Ba7Nb4MoO20 by direct measurements afforded by the Isotope Exchange Depth Profiling technique with deuterium labelling. We also report the kinetics of H/D transport through the bulk materials and across metal-ceramic interfaces with a particular interest in the behaviour of the interface between the key Pd/Pd alloy catalyst component and the hydrogen-transporting oxide ceramic material. The transport and interface behaviour information will be of significance in designing hydrogen separation and compression membranes.

Figure 1
(Digital Presentation) Renewable Itaconic Acid As a Cathode Additive Stabilizing Ni-Rich Layered Cathode Materials for Lithium-Ion Batteries
Authors: Han Yongkang Kang , Xiao Qiang Feng
Published: September 2023

Renewable materials applied in lithium-ion batteries industry has obvious advantages because of its wide range of sources and low cost. The residual lithium compounds on the surface of nickel-rich LiNi1-x-yCoxMnyO2 (Ni-rich NCM) cathodes hinder its large-scale industrial application in lithium-ion batteries. In the past, researchers proposed several approaches including coating (Al2O3, Li3PO4), water washing coupling heat treatment. These conventional approaches have been found beneficial for mitigating the residual lithium and improving electrochemical performance of high rich nickel cathode. However, most of these used conventional additions are non-renewable precious metal or salt accompanied by extra processing/handling costs. More seriously, layer Ni-rich NCM cathodes cost more than lithium iron phosphate, because transition nickel salt is expensive. Obviously, it is crucial for Ni-rich NCM cathodes to develop green and low-cost modification process.

In this work, renewable itaconic acid (IA) as a cathode addition is used to convert the residual lithium on the Ni-rich NCM cathodes into sacrificial organic lithium salts containing polar carboxylic acid and unsaturated carbon-carbon double bond to build the Li conductive cathode-electrolyte interphase (CEI) rich in organic component containing polycarbonates/polymeric specie during the electrochemical process. As a result, the capacity of the 0.5wt% IA modified NCM cathode retains 94.1 % after 90 cycles. Itaconic anhydride, an important renewable resource, is widely used in food processing and other fields because of its wide range of sources and low price. As such, our work proposes a practical approach to mitigates residual lithium issue and control CEI formation, developing high energy and long spans lithium-ion batteries by utilizing cheap and renewable organic acid.

Figure 1
(Digital Presentation) Large-Scale Synthesis of Nanoporous Tungsten Oxide for Supercapacitor Application
Authors: Bansal Neetu , Kumar Nitish , Raghunath Salunkhe Rahul
Published: September 2023

The development of materials delivering high specific capacitance and energy density is a major challenge for supercapacitors. Due to high redox activity, several metal oxides like RuO2, MnO2, MoO3, Fe3O4, WO3 and CoOx have been broadly utilized as the active material for pseudo-capacitors. Among these, tungsten oxide (WO3), being less toxic, chemically stable, and abundantly available, has become a potential candidate and is widely investigated for pseudo-capacitors. However, some modifications are required to bring its performance to a commercial scale. Various approaches like composites with carbon and other oxides, doping, confinement, and porosity improvement are followed to improve their performances. But there is a need to find the potential of solely WO3 for supercapacitors. Looking forward to it, we have synthesized highly porous pure WO3 using the solution-based nanoprecipitation method. Our approach offers the possibility of large-scale production of porous materials with tunable pore sizes and structures compared to the traditionally used solvent evaporation-induced self-assembly (EISA) method. Herein, we used PS-b-PAA block copolymer as pore creating agent, which was removed after giving thermal treatment. The prepared material was analyzed using Brunauer-Emmett-Teller (BET) and exhibited a high specific surface area of 55.5 m2 g-1 with an average pore diameter of 3.7 nm. A detailed crystallographic and morphological analysis of these materials was carried out to check the feasibility of our material for energy storage applications. Furthermore, electrochemical investigations were carried out in 3E and 2E device configurations. The electrochemical studies demonstrate that porous WO3 has achieved a specific capacitance of 555 F g-1 at 10 mV s-1 scan rate.

Figure 1
Solid-State Electrochemistry on Supramolecular Assemblies with Strong Isotropic Property
Authors: Awaga Kunio
Published: September 2023

It has been mathematically proven that only honeycomb, diamond, and K4 lattices have a special symmetry called "strong isotropy". Note that crystallographic symmetry is determined only by the position of atoms, while strong isotropy is governed by both the position of atoms and bonds. The K4 lattice, called by various names such as gyroid lattice and srs network, is characterized by the fact that it exhibits chirality. It is recognized that their mathematically-defined “line graphs” correspond to kagome, hyper-kagome, and pyrochlore lattices, respectively, which are well known as spin frustration lattices. This relation suggests that the materials with the strong isotropic lattices possess “hidden” frustration. It is also noteworthy that the band structure of the three lattices contains exotic band dispersions such as Dirac cones due to their lattice symmetry, and that they possess porous structures. From this perspective, we proposed to form the supramolecular assemblies with the with strong isotropic property, and to carry out electrochemical valence control for realizing exotic physical properties such as Dirac electron, spin frustration, etc.

In this presentation, we will explain our previous works on the solid-state electrochemistry of LiPc as an introduction. Then, we will report the rational synthesis of the molecule-based honeycomb and K4 structures, using MOF/COF- and supramolecular-chemistry, the nanohybridization using their porous structures, the physical properties such as spin frustration and circularly polarized luminescence, and the solid-state electrochemical redox control on them without destroying the original frameworks.
Exploration of Alkyl Group Effects on the Molecular Packing of 5,15-Disubstituted Tetrabenzoporphyrins Toward Efficient Charge-Carrier Transport
Authors: Yamada Hiroko , Suzuki Mitsuharu
Published: September 2023

In an effort to expand the diversity of organic semiconductors, tetrabenzoporphyrin (BP) derivatives were developed as active-layer components of organic electronic devices. BP is characterized by its large, rigid two-dimensionally (2D) extended π-framework and therefore is promising as a core building unit of organic semiconductors [1,2]. Herein, we demonstrate that BP derivatives can afford field-effect hole mobilities of >4 cm2 V−1 s−1 upon careful tuning of substituents [3]. Comparative analysis of a series of 5,15-bis(n-alkyldimethylsilylethynyl)tetrabenzoporphyrins reveals that linear alkyl substituents disrupt the π−π stacking of BP cores. The n-octyl and n-dodecyl groups have the best balance between high solution processability and minimal π−π stacking disruption, leading to superior hole mobilities in solution-processed thin films. The resulting thin films show high thermal stability wherein the field-effect hole mobility stays above 1 cm2 V−1 s−1 even after heating at 160 °C in air, reflecting the tight packing of large BP units. These findings will serve as a good basis for extracting the full potential of 2D extended π-frameworks and thus for increasing the structural or functional diversities of high-performance organic semiconductors.

References

[1] K. Takahashi, B. Shan, X. Xu, S. Yang, T. Koganezawa, D. Kuzuhara, N. Aratani, M. Suzuki*, Q. Miao*, H. Yamada*, Engineering Thin Films of a Tetrabenzoporphyrin toward Efficient Charge-Carrier Transport: Selective Formation of a Brickwork Motif. ACS Appl. Mater. Interfaces 2017, 9, 8211-8218.

[2] J. Zhu, H. Hayashi*, M. Chen, C. Xiao, K. Matsuo, N. Aratani, L. Zhang, H. Yamada*, Single crystal field-effect transistor of tetrabenzoporphyrin with one-dimensionally extended columnar packing motif exhibiting efficient charge transport property J. Mater. Chem. C 2022, 10, 2527-2531.

[3] E. Jeong, T. Ito, K. Takahashi, T. Koganezawa, H. Hayashi, N. Aratani, M. Suzuki*, H. Yamada*, Exploration of alkyl-group effects on the molecular packing of 5,15-disubstituted tetrabenzoporphyrins toward efficient charge-carrier transport. ACS Appl. Mater. Interfaces 2022, 14, 32319-32329.
Phthalocyanine-Based Organic Thin Film Transistors as a Platform for Cannabinoid Sensors
Authors: Lessard Benoit
Published: September 2023

With a growing international trend of Cannabis legalization, there is a present need for on-the-spot, low cost, and rapid differentiation of cannabinoids. The two primary cannabinoids, Δ9-tetrahydrocannabinol (THC) and cannabidiol (CBD), obtained from Cannabis, elicit very different pharmacological effects necessitating consumer and industry methods for their detection and rapid speciation. CuPc and F16-CuPc, well characterized p- and n-type semiconductors respectively, are used as the OTFT semiconducting layer in combination with a cannabinoid-sensitive chromophore allowing for the differentiation of THC and CBD. Device analysis of pre- and post-pyrolyzed rapid plant extract samples was able to predict the THC/CBD ratio with HPLC accuracy. Spectroelectrochemistry was used to probe molecular interactions between cannabinoids with and without a cannabinoid sensitive chromophore against a variety of Pcs. Spectroelectrochemical changes to the Q-band region of the Pc spectra in the presence of analytes was related to modified ratios of Pc-Pc orientations in solution, streamlining material selection, reducing manufacturing burden, and expediting sensor development. 2D-NMR was used to further elucidate unique Pc-Pc and Pc-analyte interactions, providing additional insight on atomic level interactions. Through altered Pc-Pc orientations, analytes can induce physical alterations to Pc thin-film morphology and structure, consequently, modifying electrical performance beyond charge trapping effects. Pc peripheral and axial substitutions allow an additional level of Pc tunability and their relationship with analyte interactions, film structure, and OTFT sensing performance was explored.

We established relationships between thin-films of phthalocyanines (Pcs) with a variety of central, peripheral, and axial substituents and their response to THC. X-Ray diffraction and UV–vis absorption spectroscopy measurements demonstrate significantly altered film morphologies and the formation of new crystal orientations in response to analytes, which are corroborated by scanning electron microscopy. With exposure to THC, aluminium chloride Pc generates the largest physical film changes as well as the largest changes in OTFT performance. These findings have implications for Pc-based OTFT sensor design, suggesting that the semiconducting Pc thin-film morphologies are not static in the presence of analytes, and that the sensing response is driven both by strong analyte-Pc coordination and bulk film restructuring to accommodate these interactions.

References

Advanced Functional Materials, 2021, ASAP, doi:10.1002/adfm.202107138

ACS Appl. Mater. Interfaces, 2020, 12, 45, 50692–50702

ACS Sensors, 2019, 4, 10, 2706-2715.

Figure 1
Catch Them All! a Color Catcher Protocol for Colorimetric Sensors Based on Charged and Neutral Porphyrinoids
Authors: Caroleo Fabrizio , Magna Gabriele , Nardis Sara , Catini Alexandro , Di Natale Corrado , Paolesse Roberto
Published: September 2023

Color Catcher® (CC) is widely used to prevent the release of color while washing clothes at a rather high temperature in the washing machine, but it has recently been demonstrated to be an interesting cheap support for the development of optodes. CC is a cellulose-based material with a polymer having positively charged groups (cationic polymer)or hosting small molecules positively charged, which act as traps for negatively charged tissue dyes. For this reason, CC is an excellent solid support for selected negatively charged dyes.

We have recently developed fluorometric and colorimetric optodes grafting both anionic and neutral porphyrinoids onto CC strips. They have been applied to assess both inorganic and organic pollutants in natural waters for ecological monitoring purposes.

The exploitation of CC as the solid support of functionalized strips, coupled with LED as light source and webcam as detector, allows the development of an effective, easy-to-use, and low-cost system for the detection of different analytes in an aqueous solution. These devices could represent an interesting approach for in situ analysis of water quality control.
Multi-Redox Systems Based on Boron Subphthalocyanines
Authors: Nielsen Mogens Brøndsted
Published: September 2023

Boron subphthalocyanines (SubPcs) are cone-shaped molecules comprised of three isoindole units bridged by aza-linkages and with a central boron atom containing an axial substituent. SubPcs are strong chromophores, but also redox-active molecules undergoing both reversible oxidation and reduction. By linking together SubPc units, multi-redox systems emerge that can take several redox states. Here I will show a variety of such scaffolds where SubPc units are either linked together at axial or peripheral positions by various acetylenic bridges. Bridges include various acyclic oligo(en)ynes and cyclic radiaannulenes containing both endo- and exocyclic carbon-carbon double bonds.1 The length and nature of the bridging unit determines whether the SubPc units are independent redox centers or whether there is communication between the units. Moreover, I will present structures were isoindole units of SubPc are replaced by thienopyrrole units2 as well as structures where the SubPc is linked to another redox-active unit, such as a triangulene.3 Experimentally determined redox potentials were compared to theoretically calculated ones, allowing us to move forward a reliable theoretical method for predicting redox properties.

References

a) H. Gotfredsen, L. Broløs, T. Holmstrøm, J. Sørensen, A. V. Mu
ñ
oz, M. D. Kilde, A. B. Skov, M. Santella, O. Hammerich, M. B. Nielsen, Org. Biomol. Chem.
2017, 15, 9809-9823; b) L. Broløs, M. D. Kilde, M. B. Nielsen, Org. Biomol. Chem.
2020, 18, 6077-6085; c) A. U. Petersen, M. G. Rasmussen, M. C. H. Thomsen, A. Ceuninck, M. B. Nielsen, Arkivoc
2020, vii, 145-157; d) H. Lissau, C. L. Andersen, F. E. Storm, M. Santella, O. Hammerich, T. Hansen, K. V. Mikkelsen, M. B. Nielsen, Chem. Commun.
2018, 54, 2763-2766.

H. Gotfredsen, F. E. Storm, A. V. Muñoz, M. Santella, A. Kadziola, O. Hammerich, K. V. Mikkelsen, M. B. Nielsen, Chem. Eur. J.
2017, 23, 16194-16198.

M. G. Rasmussen, M. F. Jespersen, O. Blacque, K. V. Mikkelsen, M. Juríček, M. B. Nielsen, Energy Sci. Eng.
2022, 10, 1752-1762.

Figure 1
From Formyl-Corroles to Non-Aromatic Porphyrinoids
Authors: Kielesiński Łukasz , Ghosh Abhik , Monaco Guglielmo , Gryko Daniel T.
Published: September 2023

In 1998, it would have been impossible to imagine that only 20 years later the chemistry of one of corroles would expand to create an independent field of study. The synthesis of corroles has undergone incredible changes. From multistep strategies that attracted only practitioners in the field, the procedure has been transformed into a one-pot process from commercially available reagents. The synthesis of meso-substituted corroles evolved quickly during the first seven years after Paolesse’s and Gross’s discovery [1,2]. The methodology which led to trans-A2B-corroles (i.e., corroles bearing substituents A at positions 5 and 15 and substituent B at position 10) from dipyrranes and aldehydes was discovered in 2000 and optimized several times prior to 2006, when we discovered that as long as aldehydes and dipyrranes were relatively small and/or hydrophilic, performing this reaction in a mixture of water and methanol in the presence of HCl allowed the yields to increase from 6-30% to ~55% [3,4]. The synthetic revolution made it possible to try risky ideas in diverse areas of materials chemistry and in various biology- and medicine-oriented applications. Multiple challenges still remain in the preparation of corroles.

One of those challenges is the preparation of corroles possessing CHO groups. Free formyl groups can be reacted with multiple nucleophiles forming more complex and more advanced structures. At the same time CHO is the reacting group pivotal in the corrole synthesis. Attempting to solve this conundrum we recently developed the synthesis of tris(4-formylphenyl)corrole in straightforward fashion. During the realization of this project we discovered that 10-(2-formylphenyl)corrole undergoes intramolecular Friedel-Crafts reaction leading to non-aromatic, π-expanded corrole. This divalent macrocycle possess intriguing photophysical properties and has an ability to form complexes with various metals.

References

Gross, Z.; Galili, N.; Saltsman, I. Angew. Chem. Int. Ed.
1999, 38, 1427−1429.

Paolesse, R.; Jaquinod, L.; Nurco, D. J.; Mini, S.; Sagone, F.; Boschi, T.; Smith, K. M. Chem. Commun.
1999, 1307−1308.

Koszarna, B.; Gryko, D. T. J. Org. Chem. 2006, 71, 3707−3717.

Orłowski, R.; Gryko, D.; Gryko, D. T. Chem. Rev. 2017, 117, 3102-3137.

Figure 1
From (Sub)Porphyrin to (Sub)Phthalocyanine: Aromaticity Signatures in the UV-Vis Absorption Spectra
Authors: Escayola Gordils Silvia , Labella Jorge , Szczepanik Dariusz W , Poater Albert , Solà Miquel , Torres Tomas , Matito Eduard
Published: September 2023

Understanding the structure-property relationship in (sub)porphyrin and (sub)phthalocyanine derivatives facilitates the design of new materials on demand. One of the main features of these systems are their optical properties, i.e. characteristic Soret and Q absorption bands, which depend on π-delocalization. A possible way to characterize differences in the π system is the theoretical description of the aromaticity, previously used to rationalize the non-optical properties of octaphyrins [1]. However, the high complexity given by the topological flexibility and the existence of multiple π-electron circuits makes it a challenging task [2]. In this work, we analyze the influence structural differences on the aromatic character and the UV/vis absorption spectra of eight (sub)porphyrinoids (Figure 1), including phthalocyanine and subpthalocyanine. We performed calculations at CAM-B3LYP/cc-pVTZ level of theory followed by global and local aromaticity descriptors, providing a qualitative relation between aromaticity and UV-vis absorption spectra. We found that the red shifts in Soret and Q bands observed for tetra/tri-isoindole systems compared to pyrrole analogs correlate with the decrease of global aromaticity due to the inclusion of the fused benzene units.

Figure 1
Synthesis and Electrochemical Properties of Hydrogenated Porphyrins: Chlorinphlorin and Tetrahydrocorrin
Authors: Dogutan Dilek K , Nocera Daniel G
Published: September 2023

Synthesis and Electrochemical Properties of Hydrogenated Porphyrins: Chlorinphlorin and Tetrahydrocorrin

Synthetic tetrapyrrolic compounds have been extensively examined including the hydrogenated forms and their metalated derivatives. The suite of compounds includes porphyrins, chlorins, bacteriochlorins, isobacteriochlorins, and corroles. Nonetheless, a host of new macrocyclic structures await discovery, and their chemistry to be explored. This talk will focus on two rare hydrogenated forms of porphyrin: tetrahydrocorrins (TDC) and a chorinphlorin. The monoanionic tetrapyrrolic macrocycle B,C-tetradehydrocorrin (TDC) resides at the 4e− and 4H+ midpoint between corroles and corrins. This chemical space remains largely unexplored due to a lack of reliable synthetic strategies. We now report the preparation and characterization of Co(II)- and Ni(II)-metalated TDC derivatives ([Co-TDC]+ and [Ni-TDC]+ , respectively) with a combination of crystallographic, electrochemical, computational, and spectroscopic techniques. The chlorinphlorin is an especially rare compound, and consequently, its formation and chemistry have eluded characterization. The rational and reproducible synthesis of the chlorinphlorin will be reported together with its characterization, including the compound’s X-ray crystal structure and redox properties. The talk highlights, despite the extensive chemistry of porphyrins and their related macrocycles, new frontiers await exploration.
Self-Assembly of Cone-Shaped Subphthalocyanines: A Theoretical Insight
Authors: Ortí Enrique , Calbo Joaquín , Aragó Juan , Gonzalez Rodriguez David , Torres Tomas
Published: September 2023

Compared to planar phthalocyanines, cone-shaped subphthalocyanines (SubPcs) exhibit axial dipole moments, giving rise to polarly ordered materials when piled up in columns, and become intrinsically chiral when properly substituted. Furthermore, owing to their rigid conic structure, SubPcs display a convex side (a head) and a concave side (a tail) and their intermolecular stacking interactions may lead to centrosymmetric head-to-head and tail-to-tail and to noncentrosymmetric head-to-tail aggregation geometries.

In this contribution, we perform a theoretical study on the aggregation modes of the C
3-symmetric boron SubPc 1, in which the central boron atom is substituted with a small, highly electronegative fluorine atom and the SubPc core is decorated with arilamide groups giving rise to 1P
and 1M
enantiomers (Figure 1). Depending solely on the solvent nature (aromatic or aliphatic), π-conjugated SubPc 1 can self-assemble either in a tail-to-tail dimer (regime A) or in a head-to-tail columnar stack (regime B), formed via a nucleation-elongation polymerization mechanism.1 Furthermore, 1P
and 1M
enantiomers give rise to homochiral assemblies with opposite helicities.2 Calculations indicate that whereas the SubPc enantiomers socially self-sort in the polymer regime, showing an alternate columnar stacking order, they reveal narcissistic self-sorting in the dimer regime, each enantiomer disclosing a strong preference to associate with itself.

References

1. M. J. Mayoral, J. Guilleme, J. Calbo, J. Aragó, F. Aparicio, E. Ortí, T. Torres, D. González-Rodríguez, J. Am. Chem. Soc.
2020, 142, 21017−21031.

2. J. Guilleme, M. J. Mayoral, J. Calbo, J. Aragó, P. M. Viruela, E. Ortí, T. Torres, D. González-Rodríguez, Angew. Chem. Int. Ed.
2015, 54, 2543–2547.

Figure 1
Porphyrins: ‘‘Smart Catalysts’’ for the Synthesis of High-Added Value Compounds
Authors: Gallo Emma , Damiano Caterina , Cavalleri Matteo , Manca Gabriele
Published: September 2023

The chemical industry needs to develop clean, efficient and selective procedures to synthesize high added-value fine chemicals and catalytic processes provide powerful tools to reach this goal. The key point to perform sustainable transformations is the choice of catalytic systems that show selectivity, activity and stability, resulting in high TOF (turnover frequency) and TON (turnover number), not to mention an efficient catalyst must be easily recovered and recycled. Based on these concepts, the employment of metal porphyrin complexes in catalysis is constantly growing due to the enormous potential of this class of molecules. Metal porphyrins are robust and their chemo-physical properties can easily be fine-tuned by varying their molecular structure to allow the use of these catalysts to selectively promote a large number of organic transformations.

We have studied in depth the employment of metal porphyrin complexes to create new C-N and C-C bonds by using organic azides[1] and diazo compounds[2] and more recently we have focused our interest also on the synthesis of high-added value fine chemicals by using waste, such as CO2, as starting material by applying 100% atom economic procedures.[3]

We will present different synthetic protocols which will also be discussed from a mechanistic point of view based on spectroscopic and theoretical studies and the identification of active intermediates. It is important to point out that mechanistic speculations are fundamental to optimize the catalytic performance of porphyrin complexes and spread out their applications in other fields of homogeneous catalysis

References

[1] Damiano, C.; Sonzini, P.; Caselli, A.; Gallo, E. Adv. Organom. Chem.
2021, 76, 145

[2] Damiano, C.; Sonzini, P.; Gallo, E. Chem. Soc. Rev.
2020
, 49, 4867

[3] a) Sonzini, P.; Damiano, C.; Intrieri, D.; Manca, G.; Gallo, E. Adv. Synth. Catal.
2020, 362, 2961. b) Damiano, C.; Sonzini, P.; Manca, G.; Gallo, E. Eur. J. Org. Chem.
2021, 2807. c) M. Cavalleri, C. Damiano, G. Manca, E. Gallo, Chem. Eur. J.
2022, e202202729. d) P. Sonzini, N. Berthet, C. Damiano, V. Dufaud, E. Gallo J. Catalysis
2022, 414, 143–154