Pointprobe

Kinetic-controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance

Physical properties of the polycrystalline materials are mostly determined by their microstructure. As the crystallization process can determine the microstructure, the nucleation, and growth can also control whether the materials will be resulted in single crystalline or polycrystalline. Along with the morphological changes, anisotropic properties of the materials can also be controlled. *

As a result, preferential orientation with advanced optoelectronic properties can enhance the photovoltaic devices’ performance. *

Although incorporation of additives is one of the most studied methods to stabilize the photoactive α-phase of formamidinium lead tri-iodide (α-FAPbI3), no studies focus on how the additives affect the crystallization kinetics. *

In the article “Kinetic-Controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance” along with the role of methylammonium chloride (MACl) as a “stabilizer” in the formation of α-FAPbI3, Sooeun Shin, Seongrok Seo, Seonghwa Jeong, Anir S. Sharbirin, Jeongyong Kim, Hyungju Ahn, Nam-Gyu Park and Hyunjung Shin point out the additional role as a “controller” in the crystallization kinetics. *

With microscopic observations, for example, electron backscatter diffraction and selected area electron diffraction, it is examined that higher concentration of MACl induces slower crystallization kinetics, resulting in larger grain size and [100] preferred orientation. *

Optoelectronic properties of [100] preferentially oriented grains with less non-radiative recombination, a longer lifetime of charge carriers, and lower photocurrent deviations in between each grain induce higher short-circuit current density (Jsc) and fill factor. *

Resulting MACl40 mol% attains the highest power conversion efficiency (PCE) of 24.1%.

The results provide observations of a direct correlation between the crystallographic orientation and device performance as it highlights the importance of crystallization kinetics resulting in desirable microstructures for device engineering. *

The electrical characterizations with atomic force microscopy (AFM) and conductive atomic force microscopy ( C-AFM) were done to measure the local conductance of FAPbI3 films. All measurements were performed under illumination (green LED) with a 1.3 V bias using a Pt-coated C-AFM probe (NanoWorld PlatinumIridium coated Pointprobe® CONTPt ). FTO was used for the conductive substrates. *

Conductive atomic force microscopy (C-AFM) indicated much more homogeneous photocurrent generation along the surface of (100) preferentially oriented layers. *

Figure 4 from Sooeun Shin et al. 2023 “Kinetic-Controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance”:
Electrical properties of (100)-oriented α-FAPbI3 thin films. a,b) Surface topography and photocurrent measurement by C-AFM of MACl10% and MACl40%. Measurements were taken under illumination (green LED) with a 1.3 V bias. Current images indicate that photocurrents were induced grain by grain, as each grain showed a distinct photocurrent. The photocurrent deviation for each grain is larger in MACl10% than in MACl40%, which shows a similar photocurrent grain by grain. c,d) Current line profile extracted from the current image (a and b). The standard deviation calculated from the magnitude of the photocurrent in each grain is displayed in the inset (0.019 and 0.014 nA for MACl10% and MACl40%, respectively). A low photocurrent was exhibited at the grain boundaries in both MACl10% and MACl40%. The dark areas measured within the current images are most likely distributed between grain edges. This may be caused by the formation of PbI2 or the loss of contact between the grain and the conducting substrate.

*Sooeun Shin, Seongrok Seo, Seonghwa Jeong, Anir S. Sharbirin, Jeongyong Kim, Hyungju Ahn, Nam-Gyu Park and Hyunjung Shin
Kinetic-Controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance
Advanced Science, Volume 10, Issue 14, May 17, 2023, 2300798
DOI: https://doi.org/10.1002/advs.202300798

Open Access The article “Kinetic-Controlled Crystallization of α-FAPbI3 Inducing Preferred Crystallographic Orientation Enhances Photovoltaic Performance” Sooeun Shin, Seongrok Seo, Seonghwa Jeong, Anir S. Sharbirin, Jeongyong Kim, Hyungju Ahn, Nam-Gyu Park and Hyunjung Shin is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/.

Flexible Polyurethane Foams Modified with Novel Coconut Monoglycerides-Based Polyester Polyols

The products of the polyurethane (PU) industry such as foams, coatings and adhesives are numerous and can be found in many areas of everyday life. *

Polyols are an essential component in the production of polyurethane. Nowadays they mostly come from petroleum products. *

In view of potential risk factors such as the running out of fossil fuels, supply chain issues, environmental concerns and economic risks it is important to develop alternatives as substitutes and supplements to the existing petroleum derived polyols. *

Vegetable oils can be used to manufacture biobased polyols and various oils such as linseed oil, rapeseed oil, canola oil, grapeseed oil, corn oil, rice bran oil, palm oil, olive oil, castor oil and soybean oil have already been used to make polyols for different purposes.*

Most of the polyols derived from vegetable oils that are already commercially available are made from soybean and castor oil and are mainly used for rigid PU foam applications. *

So far biobased materials for flexible polyurethane foams (FPUFs) have not been studied as much as their rigid counterpart. This is because, due to their chemical composition, there are limits to how much biobased materials can be used in the flexible foam without having an undesired effect on the foam’s mechanical properties. *

Coconut oil is not often used to manufacture flexible foam because the coconut oil’s high level of saturation makes it less compatible with many common methods of creating polyols, as the widely used polyol-forming processes mostly rely on the unsaturation of vegetable oil for functionalization.

To make coconut monoglycerides (CMG) or other plant-based oils usable for polyol-forming processes they need to fulfil the same structural requirements as the fossil-based products. *

In the article “Flexible Polyurethane Foams Modified with Novel Coconut Monoglycerides-Based Polyester Polyols “ Christine Joy M. Omisol, Blessy Joy M. Aguinid, Gerson Y. Abilay, Dan Michael Asequia, Tomas Ralph Tomon, Karyl Xyrra Sabulbero, Daisy Jane Erjeno, Carlo Kurt Osorio, Shashwa Usop, Roberto Malaluan, Gerard Dumancas, Eleazer P. Resurreccion, Alona Lubguban, Glenn Apostol, Henry Siy, Arnold C. Alguno, and Arnold Lubguban describe how they investigated the potential of coconut monoglycerides (CMG) as a polyol raw material specifically for flexible polyurethane foam (FPUF) applications.*

The authors synthesized high-molecular-weight polyester polyols from coconut monoglycerides (CMG), a coproduct of fatty acid production from coconut oil, via polycondensation at different mass ratios of CMG with 1:5 glycerol:phthalic anhydride.*

The resulting CMG-based polyols were shown to work well in making flexible foam. *

Fourier transform infrared (FTIR) spectroscopy and atomic force microscopy (AFM) were used for the foam characterization. *

The modification of the foam formulation increased the monodentate and bidentate urea groups, shown using Fourier transform infrared (FTIR) spectroscopy, that promoted microphase separation in the foam matrix, confirmed using atomic force microscopy (AFM) and differential scanning calorimetry (DSC). *

Atomic force microscopy (AFM) was used to evaluate the hard–soft domains phase separation of the foam. *

The atomic force microscope was operated at a scan rate of 1.0 Hz in non-contact mode using NanoWorld Pointprobe® NCHR Silicon AFM probes for standard tapping mode applications. (typical resonance frequency 320 kHz, typical force constant 42 N/m). *

It could be shown that density of the CMGPOL-modified polyurethane foams (CPFs) decreased, while a significant improvement in their tensile and compressive properties was observed. *

The investigations by Christine Joy M. Omisol et al. resulted in a new sustainable polyol raw material that can be used to modify petroleum-based foam and produce flexible foams with varying properties that can be tailored to meet specific requirements. *

Figure 11 from Christine Joy M. Omisol et al (2024) “Flexible Polyurethane Foams Modified with Novel Coconut Monoglycerides-Based Polyester Polyols”:Atomic force microscopy (AFM) phase images of CMGPOL-modified polyurethane foams (CPF) and control foam measured with a size scan of 3 μm × 3 μm showing soft and hard regions represented by red and yellow colors, respectively. The foam samples in Figure 11 that exhibited a relatively high degree of microphase separation compared with other samples are CPF-8 and CPF-20. These foams appear to have relatively lighter areas of urea-rich regions separated more prominently from the darker, polyol-rich regions. In contrast, the control foam and CPF-16 show more dispersed hard and soft domains. CPF-24 and CPF-12 are at the middle of the scale, displaying light regions but with more dispersion than CPF-8 and CPF-20. These observations from the phase images of the foam samples are in agreement with the monodentate and bidentate urea contents of the samples, wherein the foams that exhibit greater H-bonding also manifest a higher degree of microphase separation. The same results were obtained by Baghban et al. NanoWorld Pointprobe® NCHR standard tapping mode/non-contact mode silicon AFM probes were used for the foam characterizations with atomic force microscopy. — Figure 11 from Christine Joy M. Omisol et al (2024) “Flexible Polyurethane Foams Modified with Novel Coconut Monoglycerides-Based Polyester Polyols”:
Atomic force microscopy (AFM) phase images of CMGPOL-modified polyurethane foams (CPF) and control foam measured with a size scan of 3 μm × 3 μm showing soft and hard regions represented by red and yellow colors, respectively.

*Christine Joy M. Omisol, Blessy Joy M. Aguinid, Gerson Y. Abilay, Dan Michael Asequia, Tomas Ralph Tomon, Karyl Xyrra Sabulbero, Daisy Jane Erjeno, Carlo Kurt Osorio, Shashwa Usop, Roberto Malaluan, Gerard Dumancas, Eleazer P. Resurreccion, Alona Lubguban, Glenn Apostol, Henry Siy, Arnold C. Alguno, and Arnold Lubguban
Flexible Polyurethane Foams Modified with Novel Coconut Monoglycerides-Based Polyester Polyols
ACS Omega 2024, 9, 4, 4497–4512
DOI: https://doi.org/10.1021/acsomega.3c07312

The article “Flexible Polyurethane Foams Modified with Novel Coconut Monoglycerides-Based Polyester Polyols” by Christine Joy M. Omisol, Blessy Joy M. Aguinid, Gerson Y. Abilay, Dan Michael Asequia, Tomas Ralph Tomon, Karyl Xyrra Sabulbero, Daisy Jane Erjeno, Carlo Kurt Osorio, Shashwa Usop, Roberto Malaluan, Gerard Dumancas, Eleazer P. Resurreccion, Alona Lubguban, Glenn Apostol, Henry Siy, Arnold C. Alguno and Arnold Lubguban is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/4.0/.

Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy

The nature of the electrolyte cation is known to have a significant impact on electrochemical reduction of CO2 at catalyst|electrolyte interfaces. An understanding of the underlying mechanism responsible for catalytic enhancement as the alkali metal cation group is descended is key to guide catalyst development. *

In the article “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy” Liam C. Banerji, Hansaem Jang, Adrian M. Gardner and Alexander J. Cowan use in situ vibrational sum frequency generation (VSFG) spectroscopy to monitor changes in the binding modes of the CO intermediate at the electrochemical interface of a polycrystalline Cu electrode during CO2 reduction as the electrolyte cation is varied. *

Three alkali metal cations have been chosen for analysis: K+, which is the most commonly used electrolyte cation for eCO2R, Cs+, which has been shown to give the greatest enhancement for C2+ products, and Na+, which shows poorer eCO2R performance than K+ whilst maintaining appreciable levels of C-based products. The ability of VSFG to study catalyst|electrolyte interfaces without the need for modifications, as required in the spectroelectrochemical studies mentioned in the article, which can fundamentally alter the electrodes activity, makes it an important tool to assess the mechanisms occurring on the pc-Cu electrodes routinely employed for eCO2R. *

A CObridge mode is observed only when using Cs+, a cation that is known to facilitate CO2 reduction on Cu, supporting the proposed involvement of CObridge sites in CO coupling mechanisms during CO2 reduction. Ex situ measurements show that the cation dependent CObridge modes correlate with morphological changes of the Cu surface. *

The results presented in the article suggest that a high level of bridge site formation is related to, or facilitated by, the Cu restructuring that happens as a result of the use of the Cs+ cations in the supporting electrolyte. Recent reports have indicated that multiple (bridge) bound CO may be electrochemically inert but this work builds on the emerging evidence that CObridge sites are a key intermediate in the CO–CO coupling step that is required for C2+ formation during eCO2R. *

NanoWorld Pointprobe® CONTR AFM probes for contact mode atomic force microscopy (AFM) were used to characterize the morphology of the CU electrode surface before bulk electrolysis and after bulk electrolysis.*

Fig. 5 from Liam C. Banerji et al. “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy”: AFM images showing surface morphology of the Cu electrode surface (a) before bulk electrolysis, after bulk electrolysis in CO2 purged 0.5 M (b) NaHCO3, (c) KHCO3 and (d) CsHCO3 and also in (e) CO purged 0.5 M CsHCO3. Image analysis methods are described in the Experimental section.NanoWorld Pointprobe® CONTR AFM probes for contact mode atomic force microscopy (AFM) were used to characterize the morphology of the CU electrode surface before bulk electrolysis and after bulk electrolysis. — Fig. 5 from Liam C. Banerji et al. “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy”: AFM images showing surface morphology of the Cu electrode surface (a) before bulk electrolysis, after bulk electrolysis in CO2 purged 0.5 M (b) NaHCO3, (c) KHCO3 and (d) CsHCO3 and also in (e) CO purged 0.5 M CsHCO3. Image analysis methods are described in the Experimental section of the original article.

*Liam C. Banerji, Hansaem Jang, Adrian M. Gardner and Alexander J. Cowan
Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy
Chemical Science 2024, 15, 2889-2897
DOI: https://doi.org/10.1039/D3SC05295H

The article “Studying the cation dependence of CO2 reduction intermediates at Cu by in situ VSFG spectroscopy” by Liam C. Banerji, Hansaem Jang, Adrian M. Gardner and Alexander J. Cowan is licensed under a Creative Commons Attribution 3.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third-party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit https://creativecommons.org/licenses/by/3.0/.