bluuebunny/crossref_metadata_2025_split huggingface dataset:
Extreme Long Life Battery Via Atomic Layer Deposition of Solid Electrolyte on CFx Electrodes
Authors: Xing Weibing 
Published: February 2020

Modern defense and commercial applications, such as environmental sensors or implantable medical devices, require battery power sources with a wide operating temperature range, excellent reliability, an ability to resist abuse including mechanical vibrations and shock, high energy density and extreme long battery life (20 years). Unfortunately, state-of-the-art (SOA) battery power sources cannot adequately meet the combined energy density and long life requirements.
Here we present a promising method to prepare extreme long life batteries via atomic layer deposition (ALD) of solid electrolyte onto inherently high energy density and stable CFxelectrodes.
Figure 1 shows discharge voltage profiles of cells containing ALD solid electrolyte coated electrodes, overlaid with a control cell without oxide coating. The anode was metallic lithium and a conventional Li-ion electrolyte was used. The cells were discharged with a constant, one-year current rate, a relatively fast rate for 20 year service life. The ALD solid electrolyte coated cell showed no voltage delay at the initial discharge which is shown in the control cell, a phenomenon characteristic of CFx chemistry which is believed to result from the low conductivity of fresh CFx materials [1]. The elimination of the voltage delay presents significant performance advantages at start-ups. The ALD solid electrolyte coated CFxcells demonstrated more than 60mV higher discharge running voltage than that of the control cell, resulting in higher energy density and, potentially, longer battery service life.
Figure 2 shows Nyquist plots of electrochemical impedance spectroscopy (EIS) carried out for ALD solid electrolyte coated and the control cells. The ALD solid electrolyte coated cell showed a much smaller semi-circle representing a 66% smaller charge transfer resistance (leading to faster charge transfer kinetics) than the control cell. The EIS data strongly support the improved discharge performance presented above.
We will show that ALD enabled solid electrolyte coatings on CFx lead to significantly improved storage stability at extreme temperatures (e.g. 85°C) and superior after-storage discharge performance, compared with CFxwithout coating.
Our results in this study suggest solid electrolyte coating via ALD on CFx is a promising material processing methodology for extreme long life battery power sources with a complete elimination of CFx voltage delay and significantly enhanced charge transfer kinetics, energy density and electrochemical stability at extreme temperatures. Such methodology is potentially scalable economically when high throughput and high volume ALD processes are implemented.

Reference

Sheng S. Zhang, Donald Foster, Jeff Wolfenstine, Jeffrey Read, Journal of Power Sources
187, 233 (2009).

Figure 1
(Invited) Deprotonation of a Multi-Nuclear Copper Complex for High Oxygen Reduction Reaction Activity Investigated By in Situ X-Ray Absorption Fine Structure Spectroscopy
Authors: Kato Masaru , Kimijima Ken'ichi , Shibata Mari , Notsu Hideo , Ogino Kazuya , Inokuma Kiyoshi , Ohta Narumi , Oyaizu Nobuhisa , Uehara Hiromitsu , Ohba Tadashi , Uemura Yohei , Takakusagi Satoru , Asakura Kiyotaka , Yagi Ichizo 
Published: February 2020

The oxygen reduction reaction (ORR) occurs at the cathode in polymer electrolyte fuel cells (PEFCs) and its sluggish kinetics is one of the limiting factors for widespread applications of PEFCs. Although ORR catalysts have been extensively studied, platinum-based ORR catalysts with a high overpotential (>200 mV) are used even in the present state-of-the-art PEFCs.
In nature enzymatic oxygen reduction is known to occur at low overpotentials: multi-copper oxidases such as laccase catalyze ORR with an overpotential of ca. 20 mV on electrode surfaces and have been employed in enzymatic fuel cells [1-2]. These enzymes, however, are fragile and their footnotes are large, making them unsuitable for use in practical PEFCs. It is highly desirable to design and develop artificial ORR catalysts with electrocatalytic properties similar to those of the enzymes [3].
Here, we present our resent studies on in situ X-ray absorption fine structure (XAFS) spectroscopy of a dinuclear copper complex of 3,5-diamiono-1,2,4-triazole, Cu-Hdatrz [4,5], supported on a carbon black under catalytic and non-catalytic conditions to gain insights into designing highly active copper-based catalysts. It is known that the Cu-Hdatrz catalyst shows high ORR activity in basic solution [5]. Our in situ XAFS measurements in neutral and basic solutions revealed that the electron transfer from a CuI species to O2 was faster under basic conditions than that under the neutral condition and deprotonation from the triazole ligand might cause the coordination geometrical changes under a basic condition, suggesting that the deprotonated structure of the CuIactive species may be a key to understand the high ORR activity of Cu-Hdatrz or to design multinuclear copper-triazole catalysts with low overpotentials.

Acknowledgements

This work was supported by New Energy, Industrial Technology Development Organization (NEDO). XAFS experiments were performed under the approval of the Photon Factory Program Advisory Committee (Proposal No. 2010G200 and 2013G173)

References

[1] N. Mano, V. Soukharev, A. Heller, J. Phys. Chem. B, 110, 11180 (2006)
[2] M.S. Thorum, C.A. Anderson, J.J. Hatch, A.S. Campbell, N.M. Marshall, S.C. Zimmerman, Y. Liu, A.A. Gewirth, J. Phys. Chem. Lett, 1, 2251 (2010)
[3] C.H. Kjargaard, J. Rossmeisi, J.K. Norskov, Inorg. Chem.,
49, 3567 (2010)
[4] E. Aznar, S. Ferrer, J. Borras, F. Lloret, M. Liu-Gonzalez, H. Rodriguez-Prieto, S. Garcia-Granda, Eur. J. Inorg. Chem.,
2006, 5115 (2006)
[5] M.S. Thorum, J. Yadav, A.A. Gewirth, Ang. Chem. Int. Ed.,
48, 165 (2008)
How Biphthalocyanine Molecules Do Arrange on Single Crystalline Surfaces
Authors: Witkowski Nadine , Lüder Johann , Brena Barbara , Puglia Carla , Bidermane Ieva 
Published: February 2020

Phthalocyanine molecules have been the subject of a large number of investigations due to their versatile applications in the area of gas-sensing devices, photovoltaic
materials, light-emitting diodes, solar and fuel cells and molecular magnets. There is an evident need to characterize the molecular arrangement and the electronic properties of such organic molecules on the substrates, for getting a better understanding of the molecule-molecule as well as molecule-surface interactions.To achieve this goal, it is crucial to characterize the molecular arrangement of the molecules and link their physical properties to the structure of the film. In this study, we focus on the double decker biphthalocyanine of lutetium (LuPc2), which interest relies in its particular electronic properties. We have studied the growth and structure of LuPc2 molecules on clean and passivated Si(100)-2x1 and also on Au(111) surface, by molecular vapor deposition under vacuum [1, 2, 3].
We have used various surface experimental techniques such as surface differential optical spectroscopies, local probe microscopies and electron spectroscopies. We identified the growth mode and found that on the passivated silicon surface favors the self-organization of the molecules and we evidenced a strong influence of the flux during the formation of the molecular films. We could then propose the scenario for the growth of LuPc2 molecules on the two silicon surfaces, clean and passivated ones from few molecules up to about 40 nm.
On Au(111) surface, molecules are found to absorb flat on the surface forming a bilayer [5] at initial coverages whereas clusters develop for larger coverages influencing their electronic structure.
References
1. I. Bidermane et al., J. Chem. Phys. 138, 234701 (2013)
2. S. Boudet et al., Phys. Rev. B 86, 115413 (2012)
3. S. Boudet et al.,submitted to J. Phys. Chem. C
4. Z. H. Cheng et al., J. Phys. Chem. C, 111, 2007
5. I. Bidermane et al, in manuscript
Taming C60 Fullerene: Tuning Intramolecular Photoinduced Electron Transfer Process with Subphthalocyanines
Authors: Guldi Dirk M. 
Published: February 2020

Two subphthalocyanine-C60 conjugates have been prepared by means of the 1,3-dipolar cycloaddition reaction of (perfluoro) or hexa(pentylsulfonyl) electron deficient subphthalocyanines to C60. Comprehensive assays regarding the electronic features – in the ground and excited state – of the resulting conjugates revealed energy and electron transfer processes upon photoexcitation. Most important is the unambiguous evidence – in terms of time-resolved spectroscopy – of an ultrafast oxidative electron transfer evolving from C60 to the photoexcited subphthalocyanines. This is, to the best of our knowledge, the first case of an intramolecular oxidation of C60 within electron donor-acceptor conjugates by means of only photoexcitation.
Using Porphyrins in Solar Cells
Authors: Lin Ching-Yao 
Published: February 2020

In this report, we demonstrate that porphyrins with suitable chemical structures can be efficiently used in dye-sensitized solar cells (DSSC) as well as in polymer solar cells.
For DSSC in the near-IR region, a series of new porphyrins (LWP1 - 4) were prepared by attaching pyrene or 4-dimethylaminophenyl group in combination with anthracene to modify the porphyrin core.1 Significantly, DSSCs adopting the LWP1 dye exhibit energy conversion up to 800 nm without compromising the high overall efficiency. This achievement is attributed to the collective effects of the broadened and red-shifted IPCE spectra, elevated energy level at the excited states of the dyes, proper dye soaking processes, and suitable electron-donating substituent. To further this achievement, we prepared LD31 porphyrin based on LWP3.2 The device made of LD31 exhibited panchromatic spectral feature covering the whole visible region and further extending over 800 nm. When combined with an organic dye (AN-4), the performance of the LD31/AN-4 co-sensitized device attained Jsc
/mA

cm-2 = 20.3, Voc
/mV = 704, FF = 0.72, and the overall efficiency of power conversion η = 10.3 %.
For porphyrin-incorporated polymer (PPor) solar cells, a pyrene-modified porphyrin was used as a complementary light-harvesting unit (LHU). It was found that adding proper amount of the LHU increased light absorption in the 400-500 nm region, rendering the porphyrin-incorporated D-A copolymers (PPor) panchromatic light absorbers. Voc
-Jsc
trade-offs commonly seen in many D-A polymers were not found in the PPors reported in this work. This is attributed to the presence of the LHU increasing the J
sc without sacrificing the Voc
and FF of the polymer solar cells (PSCs). Thus, 8.0% PCE was observed for the PPor-2:PC71BM single-junction PSCs. Significantly, 8.6% PCE was achieved when a C-PCBSD cathodic interlayer was introduced to suppress linkage current.3

References:
1. C.-H. Wu, M.-C. Chen, P.-C. Su, H.-H. Kuo, C.-L. Wang, C.-Y. Lu, C.-H. Tsai, C.-C. Wu,* C.-Y. Lin,* J. Mater. Chem. A, 2014, 2, 991-999.
2. C.-L. Wang, J.-Y. Hu, C.-H. Wu, H.-H. Kuo, Y.-C. Chang, Z.-J. Lan, H.-P. Wu, E. W.-G. Diau,* C.-Y. Lin,* Energy Environ. Sci., 2014, 7, 1392–1396.
3. Y.-H. Chao, J.-F. Jheng, J.-S. Wu, K.-Y. Wu, M.-Ch. Tsai, C.-L. Wang, Y.-N. Hsiao, C.-L. Wang,* C.-Y. Lin,* C.-S. Hsu,* Adv.
Mater., 2014, 26, 5205-5210.
Acknowledgment: This work is supported by the Ministry of Science and Technology, Taiwan.
Structure and Electrical Properties of the Selected Crown Ether-Derivatized Bis(2,2'-bithienyl)Methanes in Langmuir-Blodgett Films
Authors: Gawecka Karolina , Noworyta Krzysztof R. , Chitta Raghu , D'Souza Francis 
Published: February 2020

Physical properties of thin films of thiophene derivatives and their polymers are greatly affected by the structure and orientation of their molecules, as well as the local environment.1 In order to obtain thin films of such compounds for practical applications, from electronic devices to chemo- and biosensors.2-3, it is important to control orientation and order of the molecules in the formed functional materials. Interesting and efficient way to allow for such a control is Langmuir and Langmuir-Blodgett technique.
In the presented contribution formation and properties of ultrathin films of the series of bis(2,2’-bithienyl)methane derivatives appended with crown ethers of varying size are presented. Uniform Langmuir films of liquid-expanded type were obtained at water-air interface for all of the used compounds. The influence of metal ions on the orientation of the molecules in the films was relatively small. Obtained Langmuir films were subsequently transferred onto the solid substrates by using Langmuir-Blodgett technique forming mono- and multilayers. In order to further elucidate structure of the formed layers AFM and STM techniques have been applied. The morphology of the multilayer films depended both on the size and orientation of the crown ether moiety in the molecules. However, in all cases formed multilayers were porous (Fig. 1). In case of monolayers, the STM studies helped to ascertain organization of the molecules in the Langmuir-Blodgett film. On the other hand the scanning tunnelling spectroscopy (STS) allowed acquisition of information about the electrical properties of the studied thiophene derivatives.

Bibliography

1. D. Hu, J. Yu, K. Wong, B. Bagchi, P. J. Rossky, P. F. Barbara, Nature,
405, (2000), 1030.
2. A. G. MacDiarmid, Angew. Chem., Int. Ed., 40, (2001),2581.
3. R. Singhal, A. Chaubey, K. Kaneto, W. Takashima, B. D. Malhotra, Biotechnol. Bioeng.,
85 (2004), 277.

Figure 1
Post-Assembly Transformations of Porphyrin-Containing Metal-Organic Framework (MOF) Films Fabricated Via Automated Layer-By-Layer Coordination
Authors: So Monica C. , Beyzavi M. Hassan , Sawhney Rohan , Shekhah Osama , Eddaoudi Mohamed , Al-Juaid Salih S. , Hupp Joseph T. , Farha Omar K. 
Published: February 2020

Metal–organic frameworks (MOFs) are hybrid materials composed of inorganic vertices connected to organic linkers. Due to the plethora of available linkers and vertices, MOFs can be easily tuned towards specific applications such as electrochromics1 and catalysis2. For some of these applications, it is desirable that MOFs be deposited as thin films. Among the most versatile and useful approaches to MOF film synthesis is layer-by-layer (LbL) coordination also called liquid-phase epitaxy.3 This approach successively and repetitively introduces solutions of each framework building block into contact with functionalized substrate and subsequently the growing MOF film. The advantage of LbL over other techniques is that MOF layer thicknesses can be controlled with molecular-scale precision. Thus, complex, multifunctional crystalline MOF structures are obtainable. The presentation will demonstrate the robustness of LbL-assembled pillared-paddlewheel-type MOF films by utilizing solvent-assisted linker exchange (SALE) or post-assembly linker metalation towards the conversion of one LbL film (L2-MOF) to another LbL film (SALEF-1 and Mg-L2-MOF).4 Notably, Mg-L2-MOF cannot be formed through other de novo strategies. While beyond the scope of our initial investigation, we believe that the ability of the known metal lability of magnesiated porphyrins should facilitate incorporation of other metal ions, including weakly bound ions, displaying interesting redox and photophysical behaviors. The findings effectively diversify the arsenal of techniques that can be deployed to obtain desired MOF films for energy conversion applications.

References

Hod, I.; Bury, W.; Karlin, D. M.; Deria, P.; Kung, C. W.; Katz, M. J.; So, M. C.; Klahr, B.; Jin, D.; Chung, Y. W.; Odom, T. W.; Farha, O. K.; Hupp, J. T. Adv. Mater.,
2014, 26, 6295.

Nguyen, H. G. T.; Schweitzer, N. M.; Chang, C., Drake, T. L.; So, M. C.; Stair, P. C.; Farha, Omar K.; Hupp, J. T., Nguyen, S. T., ACS Catal., 2014, 4, 2496.

So, M. C.; Jin, S.; Son, H.-J.; Farha, O. K.; Wiederrecht, G. P.; Hupp, J. T., J. Am. Chem. Soc., 2013, 135, 15698.

So, M. C.; Beyzavi, M. H.; Sawhney, R.; Shekah, O.; Eddaoudi, M.; Al-Juaid, S. S.; Hupp, J. T.; Farha, O. K., Chem. Commun., 2014, DOI: 10.1002/adma.201401940.

Figure 1
Photo-Assisted Chemical Sensors Based on Porphyrins Coated ZnO
Authors: Sivalingam Yuvaraj , Magna Gabriele , Catini Alexandro , Pomarico Giuseppe , Martinelli Eugenio , Paolesse Roberto , Di Natale Corrado 
Published: February 2020

Hybrid materials formed by a layer of dye molecules over a wide-band gap semiconductor are endowed by a number of properties making them appealing for optoelectronics and photovoltaic applications. However besides the conversion of visible photons into an excess of carriers, the combination of organic-inorganic materials offer other additional properties such as gas sensing.
ZnO and porphyrins are good examples of a metal oxide semiconductor and a dye molecule that give rise to a hybrid material with interesting properties. ZnO has been studied for gas sensors, optoelectronics, electronic devices, photo-anodes for dye-sensitized solar cells, and for mechanical energy harvesting. Porphyrins play fundamental roles in living systems such as the oxygen transport and charge transfer for catylitic processes in animals and the photosynthesis in plants. The rich chemistry makes them interesting for chemical sensing, indeed porphyrins are among the most versatile ligand platforms that can interact with airborne molecules by a wide spectrum of different mechanisms. The sensing properties of porphyrins are exploited for the development of artificial sensorial systems. In our group we have been interested to study the interplay of light and gas sensitivity in porphyrins-ZnO materials. We found that the conductivity of porphyrins-ZnO is both sensitive to the visible light and to donor-acceptor gases such as amines and alcohols. Furthermore, under visible light the sensitivity increases and, most interestingly, the selectivity towards electron donor species (e.g. amines) strongly increases.
In further studies we measured the surface photovoltage. This quantity that can be easily measured in the laboratory with a Kelvin probe is exploited in organic functionalized Field Effect Transistors sensors and it is also of great importance in the characterization of materials for photovoltaic applications. Kelvin probe studies, illustrates the interplay between the photosensitivity and the gas sensitivity in organic molecule functionalized semiconductor metal oxide nanostructure suggesting that volatile compounds may act as a doping to improve the photovoltaic properties of the dye-semiconductor hybrid.
The sensing properties of layers of porphyrins onto ZnO nanostructures offer a further degree of freedom for the design of sensor arrays extending the properties and the capabilities of porphyrins based sensor array in particular for medical diagnosis, the quality and control of foods and the detection of compounds signalling harmful or dangerous substances.
Advances in the Applications of Boron Tetrapyrrole and Dipyrrin Complexes
Authors: Brothers Penelope Jane 
Published: February 2020

Over the years we have developed the chemistry of boron complexes of porphyrins and corroles, and have recently made the first examples of boron calixphyrin and porphyrazine complexes. The unifying motifs are the coordination of two borons per tetrapyrrole macrocycle, with both the structural stereochemistry and the chemical reactivity dictated by the steric demands of incorporating two boron atoms within a tightly defined cavity. We are now exploring the physical properties of these classes of complexes with a view to developing applications, for example in PDT. We have also explored new chemistry of the well-known boron dipyrrins (or BODIPYs) and have developed new chemistry for directly attaching BODIPY groups to substrates that are useful in biology and materials science.

Figure 1
Nonplanr Meso-Trifluoromethyl Substituted β-Octaalkylporphyrins
Authors: Suzuki Masaaki , Hoshino Tyuji , Neya Saburo 
Published: February 2020

A trifluoromethyl (CF3) group gives a drastic perturbation to an aromatic compound owing to not only the three-dimensional steric bulkiness but also the strong electron-withdrawing characters. When introduced at sterically crowded meso-positions of β–alkyl substituted porphyrins, it is expected to cause major update of both the structural and electronic properties of the molecule. However, introduction of CF3 groups required preparation of CF3-embedded precursors such as dipyrromethanes, resulting in tedious synthetic strategies. This time, we performed the serendipitous but reproducible formation of meso-trifluoromethylated 2,3,7,8,12,13,17,18-octaalkylporphyrins by reactions of 5,5’-dicarboxy-3,3’,4,4’-tetraalkyl-2,2’-dipyrromethanes and large excess amount of trifluoroacetic acid without any additional sources of meso-carbons like aldehyde. The numbers of CF3 groups increased up to two by elongation of the reaction time and the positions of second CF3 groups varied depending on the β-substituents. The structural characterizations by X-ray diffraction analyses revealed their distorted conformations reflecting the steric repulsions around the CF3 groups. In the UV-visible absorption spectra, the lowest energy bands were red-shifted stepwise by introduction of each CF3group.
Metallation behavior was also investigated. In the cases of zinc complexes, the CF3 groups gradually changed into methoxycarbonyl (CO2Me) groups probably due to methanol in the mixture. The influence of CO2Me groups were smaller than CF3groups according to the relatively flat X-ray structures and the less-shifted absorption bands.

Reference

M. Suzuki, S. Ishii, T. Hoshino, S. Neya Chem. Lett.
2014, 43, 1563–1565.

Figure 1
Core-Modified Porphyrins Containing Novel Heterocyclic Moieties
Authors: Shen Zhen 
Published: February 2020

Aromaticity is a fundamental concept of chemical structure and bonding, which describes the enhanced stability that is derived from the delocalization of π-electrons in cyclic conjugated macrocycles. In recent years there has been a growing focus on the synthesis and characterization of ring-expanded porphyrinoids with both heteroaromatic and nonaromatic π-systems. The aromatic character can be fine-tuned through protonation, by modifying the solvent polarity and coordination environment, and by incorporating novel heterocyclic moieties as building blocks. Herein we report that the aromaticity of ring-expanded core-modified porphyrins can be tuned using dithienylethene as a building block[1]. Two stable core-modified rubyrins bearing one and two dithienylethene (DTE) units (C-1 and O-1) have been synthesized (Figure 1). With one “closed-form” DTE unit, C-1 shows aromaticity associated with its conjugated circuit of 26 pelectrons. In contrast, rubyrin O-1 containing one “open-form” DTE unit has nonaromatic properties. An analysis of the MCD spectral data and the TD-DFT and ACID calculations clearly demonstrated that the p-systems of C-1 and O-1 are aromatic and nonaromatic, respectively. The use of a dithienylethene moiety as a building block, therefore, offers a new vista of opportunities for tuning the aromaticity of ring-expanded core-modified porphyrins.

Figure 1