bluuebunny/crossref_metadata_2025_split huggingface dataset:
Electrochemical Lithium Intercalation & Exfoliation in 2D TMDs and Its in-Situ Studies
Authors: Zeng Zhiyuan 
Published: August 2024

We developed a lithium ion battery intercalation & exfoliation method with detailed experimental procedures for the mass production of 11 two dimensional TMDs and inorganic nanosheets, such as MoS2, WS2, TiS2, TaS2, ZrS2, graphene, h-BN, NbSe2, WSe2, Sb2Se3 and Bi2Te3, among them 3 TMDs achieved mono- or double layer yield > 90%. This method involves the electrochemical intercalation of lithium ions into layered inorganic materials and a mild sonication process. The Li insertion can be monitored and finely controlled in the battery testing system, so that the galvanostatic discharge process is stopped at a proper Li content to avoid decomposition of the intercalated compounds. The intercalation strategy can also be used to tune 2D TMDs’ physical and chemical properties for various applications. For example, we developed a one-step covalent functionalization method on MoS2 nanosheets for membrane fabrication, which exhibited excellent water desalination performance. For lithium intercalation mechanism, the state-of-the-art In-Situ Liquid Phase TEM is an ideal technique for identifying the phase changes during intercalation process. With self-designed electrochemical liquid cell utilized, we can directly vapture the dynamic electrochemical lithiation and delithiation of electrode in a commercial LiPF6/EC/DEC electrolyte, such as LiF nanocrystal formation, lithium metal dendritic growth, electrolyte decomposition, and solid-electrolyte interface (SEI) formation. Combining with other in-situ techniques, such as in-situ XAS, XRD and Raman, etc, the underlying lithium intercalation mechanism in TMDs were further investigated, which render us a comprehensive understanding of the intrinsic correlation between the intercalation process and TMDs.
References:
[1] R. Yang, L. Mei, et al., H. S. Shin*, D. Voiry*, Z.Y. Zeng*, Nat. Protoc., 2022, 17, 358-377.
[2] R. Yang, et al., H. S. Shin, D. Voiry, Q. Lu, J. Li*, Z. Y. Zeng*, Nat. Synth., 2023, 2, 101-118.
[2] R. Yang, L. Mei, Y. Fan, Q. Zhang, H. G. Liao, J. Yang, J. Li*, Z. Y. Zeng*, Nat. Protoc., 2023, 18, 555-578.
[3] Q. Zhang, J. Ma, L. Mei, J. Liu, Z. Li*, J. Li*, Z. Y. Zeng*, Matter, 2022, 5, 1235-1250.
[4] H. Peng, R. Wang*, L. Mei, et al., Z. Qian*, A. B. Farimani, D. Voiry*, Z. Y. Zeng*, Matter, 2023, 6, 59-96.
[5] L. Mei, et al., C. Y. Tang, D. Voiry, H. Wang*, A. B. Farimani*, Z. Y. Zeng*, Adv. Mater., 2022, 34, 2201416.
[6] R. Yang, Y. Fan, R. Ye, Y. Tang, X. Cao*, Z. Yin*, Z. Y. Zeng*, Adv. Mater. 2021, 33, 2004862.
[7] R. Yang, Y. Fan, et al., Q. Lu, Q. Wang,* J. C. Yu,* Z. Y. Zeng*, Angew. Chem. Int. Ed., 2023, e202218016.
[8] B. Tian, D. Ho*, J. Qin, et al., D. Voiry, Q. Wang*, Z. Y. Zeng*, Prog. Mater. Sci., 2023, 133, 101056.
[9] R. Yang, et al., Z. Y. Zeng*, Photocatalysis with atomically thin sheets, Chem. Soc. Rev., 2023, 52, 7687.
(Invited) Activating Nitrogen for Electrochemical Ammonia Synthesis: Modeling the Effects of Electrified Interfaces on π-Backbonding Molecules
Authors: Aubry Taylor , Clary Jacob M , Miller-Link Elisa , Vigil-Fowler Derek , van de Lagemaat Jao 
Published: August 2024

Electrocatalysts are expected to play a pivotal role in shaping our future sustainable energy landscape by enabling storage of renewable energy and its conversion into globally important chemicals. Computational simulations yield mechanistic insights that have supported catalyst discovery and optimization. However, the complexity of electrocatalyst interfaces has necessitated the development of quantum chemical methods that can accurately model these effects at reasonable computational cost.
In this work, we employ grand canonical density functional theory (GC-DFT) to capture the nuanced effects of applied potential on a solvated catalyst interface, specifically focusing on the nitrogen reduction reaction (NRR) at sulfur vacancies in 1T'-phase MoS2. In the canonical method, the widely used the computational hydrogen electrode (CHE) predicts that adsorbed N2 structure properties are potential independent. In contrast, GC-DFT calculations reveal that reductive potentials activate N2 towards electroreduction by modulating backbonding strength, lengthening the N–N triple bond, and reducing its bond order. Similar trends are identified for CO, a classic backbonding ligand, suggesting broader relevance of this mechanism to diverse electrochemistries involving backbonded adsorbates. Furthermore, reductive potentials are required to make the subsequent N2 hydrogenation steps favorable, but concurrently destabilize both N2 and hydrogen adsorption.
Our findings demonstrate that GC-DFT facilitates the comprehensive modeling of these phenomena, underscoring their collective implications in predicting electrocatalyst selectivity for the nitrogen reduction reaction and potentially other reactions. This research contributes valuable insights into the design and optimization of electrocatalysts for sustainable energy conversion.

Figure 1
Ionic 2D Materials
Authors: Ruiz Eliseo 
Published: August 2024

2D materials are an exciting topic with a wide variety of applications in many research fields, from optoelectronics, photonics or qubit devices to catalysis. So far, these layered nanoscopic materials have been obtained by different procedures. In top-down approaches, from simple mechanical "Scotch tape" exfoliation to liquid exfoliation to break the weak non-covalent interactions between layers. In this project, the challenge was to obtain 2D flakes of a 3D ionic starting material with cubic rock salt structure (e.g. alkali halides NaCl, NaF, KCl, KF or CsF). They will have physical properties with substantial differences from those of known 2D materials. For example, there are few large bandgap 2D materials, almost exclusively BN layers. The BN bulk system has a band gap around 4 eV and its monolayer 6 eV, while the employed alkali halides in this project, the bulk vales are 10.0 eV (CsF), 10.9 eV (KF), 11.7 eV (NaF), KCl eV (8.5) and eV NaCl (8.6). This will open many applications that are now only restricted to BN layers. The crucial point is how it is possible to exfoliate an isotropic 3D material with ionic interactions in three spatial directions.(1,2) The intercalation of bromine molecules in CsF was corroborated, many years ago, by X-ray single-crystal diffraction.(1,3, see Figure) The intercalated structure is analogous to that of other conventional 2D materials; for example, graphene also with bromine molecules. This intercalation into the 3D structure of the alkali halide has two effects, one is to generate an anisotropic 2D structure with alternated monoatomic CsF layers and layers of Br2 molecules. The second important effect is that now for the exfoliation of the CsF-Br2 compound, only the non-ionic F···Br-Br interactions must be broken. Preliminary DFT calculations indicate that such contact energies are of the same order of magnitude as other non-covalent interactions of common 2D materials.
The intercalation of such 2D materials has been performed by the intercalation of Br2 and IBr molecules combined with different exfoliation techniques (sonication-centrifugation, ball milling, microwaves..). The characterization of the 2D flakes has been performed using Atomic Force Microscopy. The final goal of this project is to make a profit from the large gap of such 2D systems for optoelectronic properties, such as single-photon emission.
(1) Desmarteau, D. D.; Grelbig, T.; Hwang, S. H.; Seppelt, K., Angewandte Chemie-International Edition in English
1990,
29 (12), 1448-1449
(2) Ruiz, E.; Alvarez, S., Journal of the American Chemical Society
1995,
117 (10), 2877-2883.
(3) Drews, T.; Marx, R.; Seppelt, K., Chemistry-a European Journal
1996,
2 (10), 1303-1307.

Figure 1
Activation/ Deactivation of Surface States of Heterostructure (Anatese-TiO2/Au) Via Addition of Materials with High Band Gap, Rutile TiO2 (R-TiO2) or Low Band Gap Silicon (Si), and Fabrication Strategy
Authors: Gyanprakash Maurya , Sharma Gyan , Behra Dilip Kumar , Upadhyay Arun , Pala Raj Ganesh 
Published: August 2024

The addition of high band gap or low band gap material not only modulates the optical absorption cross-section but also affects the surface state reactivity of heterostructure towards the photoelectrochemical (PEC) water splitting. Further, the deposition strategy to assemble the heterostructure also affects the effectiveness of the heterostructure. To explore such issues, we fabricated the two sets of heterostructures containing (A-TiO2, R-TiO2) and (Si, A-TiO2) via the click chemistry approach through two different strategies, i.e., layer-by-layer heterostructure (LLH), and randomly deposited heterostructure. In LLH strategy, only the addition of high band gap material R-TiO2 enhances the reactivity of the surface states. On the other hand, the addition of the low band gap material Silicon (Si) hampers the reactivity of the surface states of the heterostructure deposited via the LLH. Further, by changing the deposition strategy to RDH, the reactivity of surface states diminishes by adding either the high band gap or the low band gap material. These observations were rationalized from the framework of band structure/band-alignment in the heterostructure and also via electrochemical impedance spectroscopy (EIS).
In LLH, the addition of the A-TiO2 quenches electrons from the conduction band (CB) of R-TiO2, and the holes of A-TiO2 are transferred to R-TiO2. The holes from R-TiO2 participate in activating the surface states present at the surface. On the other hand, the addition of silicon to LLH, having CB above the CB of A-TiO2, does not allow the electrons to transfer from A-TiO2 to Si; hence, the CB electrons from A-TiO2 transfer to surface states, which enhances the energy level of surface states, making it more negative than the VB of Si. The negative shift of surface states of A-TiO2 makes it the recombination center. Interestingly, changing the fabrication strategy from LLH to RDH makes the nature of surface states from reactive to recombination states due to the interfacing of all materials with the underlying substrates.
EIS was utilized to measure and analyze the low-frequency capacitance due to the reactive surface state. The low-frequency capacitance of LLH with A-TiO2 shows the maxima at onset potential, confirming the role of reactive surface states. On the contrary, low-frequency capacitance increases monotonically for LLH with Si addition, showing the effect of recombination surface states. Overall, the study provides pointers on the interplay between band positions and electron-hole separation in heterostructures and how they can be effectively used to enhance surface reactivity in PEC water splitting.
(Invited) Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System
Authors: Sarma D. D. 
Published: August 2024

3-dimensional hybrid halide perovskites have been intensely researched because of their extraordinary optoelectronic properties with spectacular quantum efficiencies arising primarily from their suitable bandgaps to harvest the solar spectrum, low excitonic binding energies, and low-cost synthetic processes. However, stabilizing these materials under real-life operating conditions has proven to be a challenge, leading to extensive explorations of lower dimensional analogous hybrid halide materials that are often more stable, though generally having considerably higher bandgaps and excitonic binding energies. I shall present some of our investigations leading to the synthesis of a highly moisture-stable 2-dimensional hybrid lead halide material with the lowest bandgap and exciton binding energy within this class of compounds.1 I shall detail the origin of such a low bandgap and exciton binding energy, identifying the most critical control parameters to determine these properties. In addition, I shall also present preliminary results to suggest the beneficial impacts of incorporating the same organic ligand while making a solar photovoltaic device based on three-dimensional hybrid lead halide perovskites.
Reference:

Debasmita Pariari, Sakshi Mehta, Sayak Mandal, Arup Mahata, Titas Pramanik, Sujit Kamilya, Arya Vidhan, Tayur N. Guru Row, Pralay K. Santra, Shaibal K. Sarkar, Filippo De Angelis, Abhishake Mondal, and D. D. Sarma, Realizing the Lowest Bandgap and Exciton Binding Energy in a Two-Dimensional Lead Halide System, J. Am. Chem. Soc. 145, 15896 (2023).
(Invited) Plasmonic Nanofabrication of Chiral Nanodisk Ensembles
Authors: Tatsuma Tetsu , Ishida Takuya , Kameoka Yuri 
Published: August 2024

Chiral plasmonic nanostructures attract attention because those could be applied to enantioselective chemical sensors, optical isolators, light sources for circularly polarized light (CPL), metasurfaces, and metamaterials. In many cases, chiral plasmonic nanostructures are fabricated by a top-down method such as electron beam lithography (EBL). Since EBL is time-consuming and expensive, we have developed photoelectrochemical methods in which a site-selective reaction is driven by optical near field generated around anisotropic metal nanoparticles under right- or left-CPL. As anisotropic metal precursors for preparation of chiral nanoparticles, we have used gold or silver nanocuboids, nanorods, nanocubes, and triangular or hexagonal nanoplates so far.1-5 In the present work we demonstrate that laterally isotopic, circular nanodisks can also be used as precursors for the preparation of chiral nanostructures.
We prepared ensembles of circular gold nanodisks on a glass plate by a nanosphere lithography method. A glass plate was coated with a gold thin film, and an array of polystyrene spheres (500 nm diameter) was prepared on the gold film. The polystyrene spheres were etched by oxygen plasma, and the exposed gold film was etched by argon ion milling. As a result, an ensemble of gold nanodisks (~200 nm diameter) was obtained. Each nanodisk was capped with a polystyrene cone, and the cap was removed by sonication in toluene if necessary. We used both capped and uncapped nanodisk ensembles. The ensemble was irradiated with visible right- or left-CPL in the presence of silver ions and sodium citrate. The obtained Au-Ag nanostructures exhibited circular dichroism (CPL), indicating that the nanostructures have chirality. Initial deposition at arbitrary site may break the geometric symmetry, resulting in the growth into chiral structures.

Saito, K.; Tatsuma, T. Nano Lett.
2018, 18, 3209–3212.

Morisawa, K.; Ishida, T.; Tatsuma, T. ACS Nano
2020, 14, 3603–3609.

Shimomura, K.; Nakane, Y.; Ishida, T.; Tatsuma, T. Appl. Phys. Lett.
2023, 122, 151109.

Homma, T.; Sawada, N.; Ishida, T.; Tatsuma, T. ChemNanoMat
2023, 9, e202300096.

Ishida, T.; Isawa, A.; Kuroki, S.; Kameoka, Y.; Tatsuma, T. Appl. Phys. Lett.
2023, 123, 061111.
(Invited) Novel Q Carbon Anodes for Sodium-Ion Batteries
Authors: Paranthaman Mariappan Parans , Pethe Saurabh , Sahoo Siba Sundar , Sun Xiao-Guang , Narayan Jagdish 
Published: August 2024

The main goal of this research is to develop low-cost anodes for sodium-ion batteries. Lack of standard carbon intercalation/insertion anode for sodium-ion batteries has greatly hindered its application. Two types of Q carbons have been studied as a potential anode material for sodium-ion batteries. Q1 carbon exhibits a high initial columbic efficiency of 81% but has a low-capacity retention of less than 60%. Whereas Q2 carbon has a low initial columbic efficiency of 58% but has a high-capacity retention of 81%. Q2 exhibited a stable capacity of 168 mAh/g at a cycling rate of C/3 which is comparable to other high performing hard carbon anodes. This work will discuss in detail about the synthesis procedure, microstructural and electrochemical performance of the Q carbons. This study reports the successful pathway of using Q carbon as a promising anode for sodium ion batteries.
ACKNOWLEDGEMENTS
This research was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.
Exploration of Synthesis and Coordination Chemistry of Thiazole-Containing Calix[3]Pyrroles
Authors: Shibata Kotaro , Shibata Kotaro , Pati Narendra N. , Inokuma Yasuhide 
Published: August 2024

Calix[n]pyrroles have been used as powerful and specific receptors and as extractants for anions and ion pairs over the past 20 years. In the recent past, calix[4]pyrroles have been used as systems that can move ions and ion pairs over lipophilic membranes [1]. Unfortunately, the coordination chemistry of calix[n]pyrroles hardly explored. The ring-contracted analog of calix[n]pyrrole, calix[3]pyrrole, was synthesized and recently published [2]. The structure of calix[3]pyrrole and its analogues is strained, and they show an appealing strain-induced ring expansion response. On the other hand, the synthesis of calix[3]pyrrole requires multistep reactions including cyclization of hexaketone precursor and Paar–Knorr synthesis with the total yield of 4%. Extended use of calix[3]pyrrole analogues necessitates further refinement of the synthesis process.
Here, we demonstrate the synthesis of new calix[3]pyrroles analogue, calix[1]pyrrole[2]thiazole (3). Direct macrocyclization between bis(α-bromoketone) and 2,2-dimethylpropane (bis-thioamide) produced the calix[1]furan[2]thiazole (1), with 60% yield. The furan unit of 1 was converted into pyrrole to give calix[1]pyrrole[2]thiazole 3 (Figure 1).
Single-crystal X-ray analysis revealed a cone-shaped conformation of calix[1]pyrrole[2]thiazole 3, with all three heterocycles pointing in the same direction through strong intramolecular hydrogen bonding. However, unlike calix[3]pyrrole, calix[1]pyrrole[2]thiazole was completely stable under acidic conditions, which may be due to the basic nature of the thiazolimine units.
Metal coordination of calix[1]pyrrole[2]thiazole was attempted and its Zn(II), Ag(I) and Pd(II) complexes were obtained by appropriate metalation procedures. The central metal ion of the Zn(II) complex is coordinated by a conical 3 and an axial ethyl group to behave as a monoanionic tridentate ligand. In contrast, it acts as a bidentate neutral ligand for Pd(II) or Ag(I) complexation. The synthesis of meso-aza calix[1]pyrrole[2]thiazole is in progress.

Figure 1
Elucidating the Hydrogen Evolution Reaction Mechanism of Immobilized Iron Porphyrin Electrocatalysts
Authors: Heppe Nils , Gallenkamp Charlotte , Snitkoff-Sol Rifael Z , Paul Stephen Daniel , Segura Salas Nicole , Potapkin Vasily , Jafari Atefeh , Leupold Olaf , Schuenemann Volker , Elbaz Lior , Krewald Vera , Kramm Ulrike I. 
Published: August 2024

Based on global warming our society need to change towards CO2 free or neutral options of energy supply. The hydrogen economy plays an important role in providing and utilizing green hydrogen. While platinum is the best-known catalysts for the hydrogen evolution reaction (HER), alternatives are required that are sustainable and free of platinum group metals (PGMs).
Metal-nitrogen-carbon (MNC) catalysts have shown promising activity for the HER [1], however, often beside catalytically active MN4 centers they contain side phases that hinder mechanistic insights. The inhomogeneity in composition is based on the usual preparation approaches, that involve in minimum one pyrolysis or heat-treatment step. To avoid side phases, we focused on immobilized iron porphyrin model complexes and explored there the HER.
In this work, I will present our results associated with a substituent variation [2] and in-depth characterization by post-mortem and in situ approaches using different nuclear resonance techniques [3]. On the basis of this, we identified different species associated with the reaction cycle and the rate limiting step.
The knowledge on this will help further improvement of the porphyrinic system for HER and validation to what extent a similar mechanism applies after the pyrolysis.

References

[1] A. Shaharei, A. Moradabi, I. Martinaiou et al., Elucidating the origin of hydrogen evolution reaction activity in mono and bimetallic Metal- and Nitrogen-doped Carbon Catalysts (MeNC), ACS Appl. Mater. Interfaces 2017, 9, 25184−25193.
[2] N. Heppe, C. Gallenkamp, S. Paul et al., Substituent effect in iron porphyrin catalysts for the hydrogen evolution reaction, Chem. Europ. J. 2023, 29(19) e202202465.
[3] N. Heppe, C. Gallenkamp, R. Snitkoff-Sol et al., Applying Nuclear Forward Scattering as in situ and operando tool for the characterization of FeN4 moieties in the hydrogen evolution reaction, ChemRxiv, 2023, 10.26434/chemrxiv-2023-sk5sr.
Charged Porphyrins That Form Electronically Functional Ion Pairs and Assemblies Via
I
π–
I
π Interactions
Authors: Maeda Hiromitsu 
Published: August 2024

π-Electronic ions with appropriate geometries and peripheral substituents provide assemblies through the interactions between charged building subunits, resulting in fascinating electronic properties. Structures and properties of the assemblies can be controlled by the combined positively and negatively charged species in the assemblies.[1–3] In fact, π-electronic ion pairs comprising porphyrin-based π-electronic anions have exhibited characteristic assembling modes via
i
π–
i
π interactions and resulting electronic properties such as solid-state absorption, which was correlated with the arrangement of constituent charged π-systems, and photoinduced electron transfer.[4] Among various combinations of the porphyrin anions with porphyrin–AuIIIcomplexes as π-electronic cations,[5] the “activated” ion pair of meso-EWG (electron-withdrawing group)-substituted cation and meso-EDG (electron-donating group)-substituted anion exhibited the electron transfer in the ground state, resulting in the production of the heterodiradical in a close stacking structure as revealed by the ESR.[6] Further modifications of charged porphyrins and analogs have been examined for the electronic properties that are derived from ion pairing.
[1] Recent reviews: (a) Haketa, Y.; Yamasumi, K. et al. Chem. Soc. Rev.
2023, 52, 7170; (b) Haketa, Y. et al. Responsive Mater.
2023, 1, e20230018. [2] Recent reports on ion pairs and assemblies: (a) Yamasumi, K. et al. Angew. Chem. Int. Ed.
2023, 62, e202216013; (b)Sugiura, S. et al. J. Am. Chem. Soc.
2023, 144, 8122; (c) Haketa, Y. et al. Chem. Sci.
2024, 15, in press (DOI: 10.1039/d3sc04564a). [3] Selected reports on pyrrole-based π-electronic molecules: (a) Haketa, Y. et al. J. Am. Chem. Soc.
2020, 142, 16420; (b) Ishikawa, S. et al. under revision. [4] Sasano, Y.; Tanaka, H. et al. Chem. Sci.
2021, 12, 9645. [5](a) Haketa, Y. et al. iScience
2019, 14, 241; (b) Nakajima, R. et al. to be submitted; (c) Maruyama, Y. et al. to be submitted. [6](a) Tanaka, H. et al. J. Am. Chem. Soc.
2022, 144, 21710; (b) Tanaka, H. et al. Chem. Eur. J.
2023, 29, e202203957.