bluuebunny/crossref_metadata_2025_split huggingface dataset:
Phase Engineering of Two-Dimensional WS2 Nanostructures for Superior Hybrid Supercapacitors
Authors: Shinde Pragati A. , Ariga Katsuhiko 
Published: August 2024

Two-dimensional (2D) tungsten sulfide (WS2) has recently emerged as a nontrivial material for electrochemical applications; however, the boundaries associated with its 1T (instability) and 2H (low electrical conductivity) phases limit its electrochemical parameters. In this work, this issue is addressed using an exclusive chemical approach to evolve a dual-phase 1T-2H WS2 heterostructure that combines two different 1T (trigonal) and 2H (hexagonal) phases directly on the current collector which demonstrated 2D transformable phase structure, large interlayer distance, and highly exposed edge active sites. A simple inert-atmosphere annealing approach under phosphorus vapors is designed to elicit a fractional phase conversion of WS2 from conventional 2H to the 1T phase, where phosphorus is accommodated in the WS2 interspace and lattice, resulting in interlayer expansion. Theoretical calculations confirmed that the 1T WS2 structure formed after phosphorus doping exhibits semimetallic feature with no band gap, thereby elucidating the high electrical conductivity. The presence of edge-enriched metallic phase and interlayer engineering of 1T-2H WS2 heterostructure validates the exceptional sodium (Na+) ion intercalation when tested in hybrid supercapacitor (HSCs) against Prussian blue analog (PBA) cathodes. As a result, the assembled HSC cell with a 1T-2H WS2 heterostructured anode and a CuFe-PBA cathode shows superior specific energy of 65.5 Wh kg-1 at a specific power of 784 W kg-1, and maintains 75% rate capability and 95.7%
cycling stability over 10,000 cycles. This work paves a technique for engineering a simple phase transition of 2D materials and sheds light on the expansion of high-performance next-generation energy storage systems.
(Invited) Exploitation of Advanced Materials and Process for Sustainable Perovskite Solar Cells
Authors: Jung Hyun Suk 
Published: August 2024

All solid-state solar cells based on organometal trihalide perovskite absorbers have already achieved distinguished power conversion efficiency (PCE) to 26.1% and further improvements are expected up to 27%. Now, the research on perovskite solar cells (PSCs) has been moving toward commercialization. To facilitate commercialization of these great solar cells, some technical issues such as long-term stability, large scale fabrication process, Pb-related hazardous materials, and environmentally-burdened toxic solvent-based process need to be solved.
This talk is dealing with our recent efforts to facilitate commercialization of perovskite solar cells. For examples, we introduce a recycling technology of perovskite solar cells, which covers the regeneration process of Pb contained perovskite layer as well as recycling process of Au electrodes and transparent conducting oxide glass [1, 2]. Also, novel strategies for recycling toxic solvents such as DFM, used in fabricating PSCs are introduced, which is critical to realize close loop recycling process of PSCs. Finally, recent studies for achieving high efficiency PSC using ecofriendly solvent are demonstrated.
Machine-Learning Accelerated Description of Polarons in 2D Lead Halide Perovskites
Authors: Graupner David , Kilin Dmitri S. 
Published: August 2024

MLFF-based MD trajectories to compute NAC and excited-state dynamics. At each stage, results based on machine learning are compared to traditional ab initio based electronic dissipative dynamics.
The limits of this method are explored as we increase the timescale of the calculation beyond those allowed by ab initio molecular dynamics and to determine the effectiveness of MLFF-MD when used for excited-state nonadiabatic dynamics simulations using atomistic models that include charge injection or when an excited-stated potential energy surface is used to account for changes due to an excitation.
Cobalt Complex of an N-Linked Carbacorrole Analog: Axial Ligand Effect on Electronic Structure
Authors: Ishida Masatoshi 
Published: August 2024

Corrole, recognized as a contracted tetrapyrrolic macrocycle featuring an α,α'-linked bipyrrole moiety, has garnered attention for its unique trianionic N4 donor environment at the inner core. This characteristic has prompted the exploration of various high-valent metal species for potential catalytic applications. In our pursuit of uncovering new reactivity in metallo-corroles, we have previously synthesized a distinct carbacorrole ligand known as N-confused/N-linked corrole analogs.[1] The former variant incorporates an inverted pyrrole moiety connected at the α and β’-linking positions, while the latter exhibits a unique linkage between the α-pyrrole ring and the pyrrolic N site. The resulting [NNNC] coordination environment of carbacorroles stabilizes distinctive organometallic species, particularly with copper(III) ions.[2]
In this study, we synthesized novel cobalt complexes featuring an N-linked carbacorrole analog with a benzo annulation, referred to as benzonorrole. The electronic structure of the ensuing complex is notably influenced by the axial ligands. The monodentate pyridine axial coordination to the cobalt norrole complex revealed unique reactivity, resulting in an oxygenated product at the inner carbon site. The oxygenated cobalt norrole complex can be characterized as a singlet Co(II) ligand radical at the ground state, as evidenced by various spectroscopic methods and magnetic susceptibility measurements. Upon substitution with a triphenylphosphine ligand, the resulting five-coordinated cobalt norrole complex was found to be stable and considered a diamagnetic cobalt(III) species, devoid of redox noninnocent character. This talk will delve into the detailed structure and electrochemical properties of these intriguing complexes.
[1] Fujino, K.; Hirata, Y.; Kawabe, Y.; Morimoto, T.; Srinivasan, A.; Toganoh, M.; Miseki, Y.; Kudo, A.; Furuta, H. Angew. Chem. Int. Ed.
2011, 50, 6855-6859; Toganoh, M.; Kawabe, Y.; Uno, H.; Furuta, H. Angew. Chem. Int. Ed.
2012, 51, 8753-8756.
[2] Maurya, Y.; Noda, K.; Yamasumi, K.; Mori, S.; Uchiyama, T.; Kamitani, K.; Hirai, T.; Ninomiya, K.; Nishibori, M.; Hori, Y.; Shiota, Y.; Yoshizawa, K.; Ishida, M.; Furuta, H. J. Am. Chem. Soc. 2018, 140, 6883-6892.
Pot-Economical Approaches to the Synthesis and Functionalization of Phthalocyanines for Clean Energy Production
Authors: Zanotti Gloria , Palmeri Federica , Raglione Venanzio 
Published: August 2024

The last decades have witnessed a growing interest in reducing the ecological and economic impact of chemical processes, with an important focus on the development of more environmentally friendly procedures and methodologies in organic synthesis. Given the extreme versatility and technological importance of phthalocyanines for a variety of applications, of which clean energy production is among the most relevant, the design and study of alternative and less-impacting synthetic approaches to the conventional ones have gained importance in the last years. Their synthesis in solution frequently requires reaction media such as high boiling point alcohols (pentanol, hexanol), dimethylaminoethanol, chlorobenzene, quinoline, and α-chloronaphthalene, most of which are toxic and non-environmentally friendly. Some green synthetic approaches based on solvothermal methods [1,2], mechanochemistry [3], or alternative sources of energy such as microwaves [4-6] and ultraviolet radiation [7], have been developed in order to minimize if not overcome this issue and provide less-impacting experimental conditions for their production. A less studied but very promising approach concerns the development of pot-economical processes, in which two or more reactions take place in the same reaction vessel. The advantage of this approach is twofold: on the one hand it significantly reduces the amount of chemicals required to synthesize and purify a target product, on the other it minimizes the total time required to obtain it. Clearly, the process must be carefully designed in order to avoid yield decreases due to side reactions.
In this contribution, the rational design of symmetrical and unsymmetrical substituted phthalocyanines by means of pot-economical approaches in solution will be shown and discussed, along with an estimation of the environmental and economic impact with respect to the related conventional procedures. Examples will be shown both of derivatization of already formed macrocycles, following a “late-stage functionalization” approach [8], and of derivatization of phthalonitriles followed by in-situ metal-templated cyclotetramerization. Furthermore, their optical and electrochemical characterization will be shown, discussed and compared with each other by relating the obtained data to their different chemical structures. Finally, examples of their implementation in the field of organic optoelectronics, with a focus on perovskite solar cells, will be presented.

D. Li et al CrystEngComm 2018, 20, 2749–2758.

D. Li, et al RSC Adv. 2021, 11, 31226–31234.

D. Langerreiter et al Angew. Chem. Int. Ed. 2022, 61, e202209033.

A. Shaabani et al Dyes Pigm. 2007, 74, 279–282.

D. Villemin et al Molecules 2001, 6, 831–844.

A.C.S. Gonzalez et al. J. Porphyr. Phthalocyanines 2020, 24, 947–958.

Y. Saito et al Chem-NanoMat 2015, 1, 92–95.

G. Zanotti et al ChemPlusChem 2020, 85, 1–12
Transforming Waste into Valuable Chemicals: CO2 Conversion Enabled by Porphyrin-Based Catalysts
Authors: Gallo Emma 
Published: August 2024

Carbon dioxide is the primary greenhouse gas responsible for global warming and the resulting climate change, which is provoking a significant increase in extreme weather events that impact our health, environment, and economy. Nowadays the scientific community is focusing many efforts on the use of CO2 as a C1 source in the synthesis of a wide range of useful products, in alignment with circular economy principles [1].
Here we report the reaction of CO2 with epoxides and aziridines, forming cyclic carbonates and oxazolidin-2-ones, by a 100% atom-efficient procedure promoted by porphyrin-based catalytic systems [2]. Considering that the contemporary presence of electrophile and nucleophile promoters is usually required for these classes of transformations, several binary and bifunctional porphyrin-based systems will be discussed with the final goal to underline the advantages of employing these systems in terms of broad applicability and eco-tolerance. Porphyrins exhibit remarkable chemical versatility, allowing for precise tuning of catalytic performances and reaction chemo-selectivity. Furthermore, the heterogenization of single-site catalysts onto solid supports enhances practical applicability [3].
In addition, synthetic protocols will also be discussed from a mechanistic point of view on the basis of spectroscopic and theoretical studies and taking into account the identification of active intermediates [4].

References

[1] A. Alok, R. Shrestha, S. Ban, S. Devkota, B. Uprety, R. Joshi J. Environ. Chem. Eng., 2022, 10, 106922.
[2] a) M. Cavalleri, C. Damiano, G. Manca, E. Gallo Chem. Eur. J., 2023, 29, e202202729. b) C. Damiano, P. Sonzini, G. Manca, E. Gallo Eur. J. Org. Chem., 2021, 2807. c) P. Sonzini, C. Damiano, D. Intrieri, G. Manca and E. Gallo Adv. Synth. Catal.
2020, 362, 2961.
[3] P. Sonzini, N. Berthet, C. Damiano, V. Dufaud, E. Gallo J. Catal., 2022, 414, 143. b) C. Damiano, A. Fata, M. Cavalleri, G. Manca, E. Gallo submitted.
[4] C. Damiano, N. Panza, J. Nagy, E. Gallo, G. Manca New J. Chem., 2023, 47, 4306.

Figure 1
Supramolecular Assembly of Nitrogen-Containing Curved π-Conjugated Molecules to Polar Crystal
Authors: Hiroto Satoru , Wakita Mana 
Published: August 2024

The chemistry of curved π-conjugated molecules has been extensively studied because of the development of their synthetic approach. Among the numerous studies, we have been engaged in nitrogen-containing curved π-conjugated molecules. These molecules have extended optical properties, redox-active behaviors, and electron-donating ability due to the electron-rich nature of nitrogen atoms. Recently, we have focused on the supramolecular assembling behavior of these compounds. For example, we have reported buckycatcher consisted of two azabuckybowls, providing two-photon absorbing host-guest complexes with fullerenes. In this presentation, we would like to show the packing behavior using π-extended azahelicenes and azabuckybowls. Our group has developed π-extended aza[5]helicene derivatives, showing brilliant emissive features. Recently, we succeeded in the synthesis of unsymmetrically substituted azahelicenes. We found that their stackings in the crystal were dependent on the substituent. X-ray diffraction analysis for all products showed π-stacked conformation with each other in the crystal (Figure 1b). In particular, azahelicenes with triisopropylsilyl groupswere found to align their dipole moments to form a one-dimensional columnar structure in the crystal. Polar crystals are expected to have applications in ferroelectric, piezoelectric, and nonlinear optical response materials. This is the first example of a polar crystal with helicenes, paving the way for novel piezoelectric organic materials.
The second topic is related to azabuckybowl. In the crystal, azabuckybowl forms a face-to-face dimer by concave-convex interaction. In this study, we prepared two types of azabuckybowl perylene bisimide (PBI) dyads connected with alkyne linkages. PBIs have also been reported to show columnar stacking in solution. We anticipated that the segregate stacking should be achieved by recognizing the difference in structures between the bowl and planar geometry. The UV/vis absorption spectra revealed the presence of intramolecular charge-transfer interaction. In addition, the concentration-dependent absorption spectra and 1H NMR spectra indicated PBI and azabuckybowl units stacked with each other independently in solution (Figure 1a). Here, we would like to discuss about the effect of the effect of molecular shape on the supramolecular assembly with the data obtained using these compounds.

Figure 1
Method to Independently Measure the Electronic and Ionic Conductivity of Zinc Slurry Electrodes
Authors: Kathan Devadharshini , Mustain William Earl 
Published: August 2024

Zn-MnO2 alkaline batteries are prevalent and reliable primary batteries due to their cost effectiveness, good safety characteristics, long shelf life and ability to deliver sustained power for continuous usage. This properties make alkaline batteries an ideal options to be used in remote controls, smoke detectors, wireless mice, toys and many portable electronic devices. Despite their advantages, the battery performance is constrained by the slurried Zinc anode. Because of this, researchers have prioritized the improvement of the anode, primarily aiming to enhance the capacity and stability of the active material. However, the actual behavior of the anode is limited by the ionic conductivity of Zinc slurry, which is several orders of magnitude lower than the electronic conductivity of the slurry. This causes the reacting front to begin at the anode-separator interface, leading to passivation of the anode, incomplete discharge and increased gassing.
The utilization of Zinc in the slurry anode can be increased by bringing the values of ionic conductivity and electronic conductivity closer together. Unfortunately, due to the redox electrolyte mechanism that moves electrons through the anode [1], the literature does not have an established method that is able to independently measure the ionic and electronic conductivity of the slurry. Before methods can be proposed to improve ionic conductivity of slurry, a method must first be devised that is able to truly measure the ionic conductivity in isolation.
In this study, a novel methodology is reported to quantify both the ionic and electronic conductivity of the slurried anode. This innovative approach aims to provide a deeper understanding of the complex interconnection between electronic and ionic conductivities of the Zinc slurry. By addressing this critical aspect, the research contributes to advancing the fundamental understanding of Zn-MnO2 alkaline batteries, potentially paving the way for significant improvements in their performance and reliability for a wide array of applications.

References

[1] E. Faegh, T. Omasta, M. Hull, S. Ferrin, S. Shrestha, J. Lechman, D. Bolintineanu, M. Zuraw and W.E. Mustain, “Understanding the Dynamics of Primary Zn-MnO2 Alkaline Battery Gassing with Operando Visualization and Pressure Cells”, J. Electrochem. Soc., 165 (2018) A2528-A2535
Aligned Semiconducting Carbon Nanotubes for Commercial Logic and RF Electronics
Authors: Jinkins Katherine , Arnold Michael S. , Foradori Sean 
Published: August 2024

Carbon nanotubes are exceptional semiconductors that offer larger current densities and faster switching than conventional Si and GaAs devices, making nanotubes promising for meeting the performance and energy efficiency needs of next-generation electronics. However, the successful commercialization of carbon nanotubes necessitates the control over semiconducting purity, alignment, packing density, and scalability. The simultaneous control of these characteristics has been a major challenge preventing the integration of nanotubes in industrial electronics and the full exploitation of their electronic properties. This talk will present an overview of recent technological developments and methods that progress towards these goals.
In these methods, semiconducting (purity of >99.99%) carbon nanotubes are deposited on target substrates via scalable alignment methods at room temperatures. These individual methods separately enable the deposition of quasi-aligned (±28°) nanotube arrays (~50 nanotubes µm-1) demonstrated across 100 mm substrates, highly-aligned (±6°) nanotube arrays (~100 nanotubes µm-1) demonstrated across 100 mm substrates, and the selective-area deposition of highly-aligned nanotube (±7°) arrays (~up to 250 nanotubes µm-1). The nanotube arrays with high packing density (~250 nanotubes μm-1) yield exceptional current densities of 2 mA μm-1 and transconductances of 1 mS μm-1 at VD of -0.6V. Importantly, due to the low-temperature nature of the deposition processes, these techniques offer a direct path towards the alignment of carbon nanotubes directly on Si and other materials, such as GaN or plastics, to enable high-performance 3D integrated circuits.
Synthesis and Modular Engineering of Porous Graphene Nanoarchitectures
Authors: Mugarza Aitor 
Published: August 2024

Bottom-up nanoarchitectonics has demonstrated the capability to control structural parameters of nanomaterials with atomic precision. The surface-assisted synthesis of graphene-based one-dimensional nanostructures à la carte distinctly illustrates the power of this concept. However, despite impressive advances in the synthesis of 1D homostructures, advancing in structural complexity faces major challenges. However, despite impressive advances in the synthesis of 1D homostructures, advancing in structural complexity faces major challenges. The functionalization of edges in nanorib-bons, an effective strategy to tailor their electronic properties and chemical interactions, is a clear example. The concept of inserting the desired functional groups or dopants in the molecular precursor often fails due to their lack of stability during the reaction path. The fabrication of heterostructures is a second example, where the challenge lies on the control of the size and distribution of their com-ponents. A third one is extending the on-surface strategy to two-dimensional structures, where examples of long-range ordered nanoarchitectures are very limited.
In this talk I will present different strategies that we have developed to overcome each one of this challenges. I will show introducing our method to synthesize a 2D nanoporous graphene, where the long-range order is achieved by the sequential growth of 1D building blocks and their posterior coupling [1]. I will continue presenting two modular strategies that lead to more complex nanoporous structures. The first consist on the molecular engineering of the coupling bridges. I will show an example where the introduction of phenyl groups in the bridges brings tunability of the quantum electronic coupling and the corresponding in-plane electronic anisotropy [2]. In a final example I will focus on intercalating different 1D ribbon components in periodic arrays for the formation of lateral heterostructure superlattices where the junction is defined with atomic precision [3]. One of the components being a N-doped ribbon, the heterostructure can also be seen as a nanoporous graphene sheet bearing N-doped pores.

References:

Moreno et al., Science 360, 199–203 (2018).

Moreno et al., J. Am. Chem. Soc. 145, 16, 8988–8995 (2023).

Tenorio et al., Adv. Mater. 2110099 (2022).
Developing Online ICP-MS Methodology for Examining Catalyst Degradation Dynamics during Electrochemical CO2 Reduction
Authors: Yan Katherine , Hannagan Ryan T. , Lee Sang-Won , Matthews Jesse E , Yap Kyra M. K. , Kamat Gaurav A. , Lee Dong Un (Daniel) , Stevens Michaela Burke , Nielander Adam C. , Jaramillo Thomas F. 
Published: August 2024

The electrochemical CO2 reduction reaction (CO2RR) provides a path towards sustainable production of carbon-based fuels and chemicals, using renewable electricity to drive the conversion of CO2 into products such as ethylene, ethanol, and methane. A challenge limiting the implementation of CO2RR is catalyst stability during operation, and greater fundamental understanding is needed to uncover the governing physical, chemical, and electrochemical factors, as well as degradation mechanisms, operative under reducing conditions. One tool that can be used for conducting such fundamental studies is online inductively coupled plasma mass spectrometry (ICP-MS). In this study, an experimental framework was developed for using online ICP-MS for time-resolved degradation studies during CO2RR conditions. Using a customized flow cell setup, we coupled an ICP-MS to a potentiostat to simultaneously apply a potential or current while evaluating dynamics and degradation for both Au and Cu catalysts. Both ionic dissolution and degradation in the form of nanoparticle detachment can be detected and analyzed. The presence of nanoparticles is indicated by spikes in ICP-MS data. The intensity of the spikes is directly related to particle size. We used ICP-MS to determine particle mass, size distribution, and cumulative mass loss over time. We found the use of ICP-MS to obtain particle size distribution gave comparable results to transmission electron microscopy (TEM) determination of particle size distribution.
Au foil as the CO2 reduction catalyst was used as a model system for detecting and quantifying degradation in situ using ICP-MS. We found Au degradation to occur in the form of nanoparticle detachment, with increasingly negative applied potential (0 V vs RHE to -1 V vs. RHE) in the presence of CO2 leading to increased number of nanoparticles in the electrolyte; however, no ionic dissolution was observed. In comparison, when the electrolyte was saturated with N2, nanoparticles detached from the electrode at a lower rate than in CO2-saturated conditions. We also examined Cu degradation under the same conditions as the Au system. Cu degradation occurs as both ionic dissolution and nanoparticle detachment, but under all conditions, Cu has less nanoparticle detachment and cumulative mass loss due to nanoparticles than Au. The developed experimental framework in this study would be translatable to a variety of electrocatalytic reactions and environments. Examination of catalyst degradation behavior in situ, including non-traditional degradation mechanisms such as nanoparticle detachment from bulk materials, can be used to obtain greater fundamental understanding of degradation mechanisms and rational design of materials with improved stability.