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1. Selective production of 5-hydroxymethylfurfural from fructose in the presence of an acid-functionalized SBA-15 catalyst modified with a sulfoxide polymer

   https://doi.org/10.1039/C9ME00093C  

   Whitaker, Mariah R.; Parulkar, Aamena; Brunelli, Nicholas A. (January 2020, Molecular Systems Design & Engineering)

   Biomass is a renewable carbon feedstock that can be converted to 5-hydroxymethylfurfural (HMF), a useful platform chemical that can be modified to produce valuable chemicals and fuels. Previous research has shown that high HMF selectivity can be achieved in organic solvents such as dimethyl sulfoxide (DMSO) because of its capability to stabilize HMF in solution, but DMSO is an undesirable solvent to use industrially as product separation from the reaction solution is difficult. Surface functionalization of porous catalysts has been shown as a method to introduce solvent-effects at the surface of heterogeneous catalysts, thus avoiding the need for high boiling solvents like DMSO. Poly(ethylene sulfoxide) (PESO) is added to the surface of sulfonic acid (SA) functionalized SBA-15 silica to obtain the bifunctional catalyst SA-PESO-SBA-15. Co-localization of the sulfoxide polymer with sulfonic acid groups inside the catalyst pores (SA-PESO-SBA-15) increased HMF selectivity to 51% from 26% obtained by monofunctional SA-SBA-15 at 27% fructose conversion in water. Additionally, this bifunctional catalyst performs best in 4 : 1 (w/w) THF : water cosolvent, a more industrially preferred cosolvent system, obtaining 79% HMF selectivity at 87% fructose conversion. Overall, these materials are promising for the selective conversion of fructose to HMF. 

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2. Stabilizing the heavily-doped and metallic phase of MoS ₂ monolayers with surface functionalization

   https://doi.org/10.1088/2053-1583/ac3f44  

   Zhang, Hanyu; Koledin, Tamara D; Wang, Xiang; Hao, Ji; Nanayakkara, Sanjini U; Attanayake, Nuwan H; Li, Zhaodong; Mirkin, Michael V; Miller, Elisa M (December 2021, 2D Materials)

   Abstract Monolayer molybdenum disulfide (MoS 2 ) is one of the most studied two-dimensional (2D) transition metal dichalcogenides that is being investigated for various optoelectronic properties, such as catalysis, sensors, photovoltaics, and batteries. One such property that makes this material attractive is the ease in which 2D MoS 2 can be converted between the semiconducting (2H) and metallic/semi-metallic (1T/1T′) phases or heavily n-type doped 2H phase with ion intercalation, strain, or excess negative charge. Using n -butyl lithium (BuLi) immersion treatments, we achieve 2H MoS 2 monolayers that are heavily n-type doped with shorter immersion times (10–120 mins) or conversion to the 1T/1T′ phase with longer immersion times (6–24 h); however, these doped/converted monolayers are not stable and promptly revert back to the initial 2H phase upon exposure to air. To overcome this issue and maintain the modification of the monolayer MoS 2 upon air exposure, we use BuLi treatments plus surface functionalization p-(CH 3 CH 2 ) 2 NPh-MoS 2 (Et 2 N-MoS 2 )—to maintain heavily n-type doped 2H phase or the 1T/1T′ phase, which is preserved for over two weeks when on indium tin oxide or sapphire substrates. We also determine that the low sheet resistance and metallic-like properties correlate with the BuLi immersion times. These modified MoS 2 materials are characterized with confocal Raman/photoluminescence, absorption, x-ray photoelectron spectroscopy as well as scanning Kelvin probe microscopy, scanning electrochemical microscopy, and four-point probe sheet resistance measurements to quantify the differences in the monolayer optoelectronic properties. We will demonstrate chemical methodologies to control the modified monolayer MoS 2 that likely extend to other 2D transition metal dichalcogenides, which will greatly expand the uses for these nanomaterials. 

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3. Interaction of Pb ²⁺ ions in water with two-dimensional molybdenum disulfide

   https://doi.org/10.1088/2515-7639/ab7ab3  

   Li, Duo O.; Gilliam, Matthew S.; Debnath, Abhishek; Chu, Ximo S.; Yousaf, Ahmed; Green, Alexander A.; Wang, Qing Hua (March 2020, Journal of Physics: Materials)

   Abstract The removal of heavy metal contaminants from water is important for public health, and recently many two-dimensional (2D) materials with high specific surface areas are being studied as promising new active components in water purification. In particular, 2D MoS₂nanosheets have been used for the removal of various heavy metals, but usually in either in complex geometries and composites, or in the chemically exfoliated metallic 1T-MoS₂phase. However, the interaction of heavy metals dissolved in water with unmodified semiconducting 2H-MoS₂is not well studied. In this paper, we report a detailed fundamental investigation of how Pb²⁺ions interact with 2H-MoS₂. We observe small solid clusters that form on the MoS₂surfaces after exposing them to Pb(NO₃)₂aqueous solutions as shown by atomic force microscopy and transmission electron microscopy, and for liquid phase exfoliated MoS₂we observe the nanosheets precipitating out of dispersion along with insoluble solid granules. We use a combination of x-ray photoelectron spectroscopy and x-ray diffraction to identify these solid clusters and granules as primarily PbSO₄with some PbMoO₄. We put forth an interaction mechanism that involves MoS₂defects acting as initiation sites for the partial dissolution in aqueous oxygenated conditions which produces MoO₄²⁻and SO₄²⁻ions to form the solids with Pb²⁺. These results are an important contribution to our fundamental understanding of how MoS₂interacts with metal ions and will influence further efforts to exploit MoS₂for water remediation applications. 

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4. Cr and CeO2 promoted Ni/SBA-15 framework for hydrogen production by steam reforming of glycerol

   Abrokwah, R; Ntow, E; Jennings, T; Stevens_Boyd, R; Hossain, T; Swain, J; Bepari, S; Hassan, S; Mohammad, N; Kuila, D (November 2023, Steel in translation)

   Ni/SBA-15 meso-structured catalysts modified with chromium and CeO2 (Ni–Cr-CeO2/SBA-15) were utilized to produce hydrogen from glycerol steam reforming (GSR). The catalysts were synthesized by a one-pot hydrothermal process and extensively characterized by analytical techniques such as N2 adsorption–desorption (BET), H2-temperature programmed reduction (H2-TPR), powder X-ray diffraction (PXRD), inductively coupled plasma-optical emission spectrometry (ICP-OES), and transmission electron microscopy (TEM). The low-angle XRD reflections affirmed that the catalysts were crystalline and possessed a 2D-ordered porosity. The BET results depicted that all the catalysts exhibited a good surface area ranging from 633 to 792m2/g, and the pore sizes were consistently in the mesoporous range (between 3 and 5 nm). TEM analysis of both calcined and spent catalysts revealed that the metal active sites were embedded in the hybrid CeO2-SiO2 support. Overall, the Ni-based catalysts exhibited higher glycerol conversion -12Ni-SBA-15–99.9%, 12Ni3CeO2-SBA-15–89.4%, and 8Ni4Cr3CeO2-SBA-15–99.7%. Monometallic 12Ni/SBA-15 performed exceptionally well, while 12Cr/SBA-15 performed poorly with the highest 71.48% CO selectivity. For short-term GSR reactions, CeO2 addition to 12Ni/SBA-15 did not have any effect, whereas Cr addition resulted in a 32% decrease in H2 selectivity. The long-term stability studies of 12Ni-SBA-15 showed H2 selectivity of ~ 64% and ~ 98% glycerol conversion. However, its activity was short-lived. After 20–30 h, the H2 selectivity and conversion dropped precipitously to 40%. The doping of mesoporous Ni/SBA-15 with Cr and CeO2 remarkably enhanced the long-term stability of the catalyst for 12Ni3CeO2-SBA-15, and 8Ni4Cr3CeO2-SBA-15 catalyst which showed ~ 58% H2 selectivity and ~ 100% conversion for the entire 60 h. Interestingly, Cr and CeO2 seem to improve the shelf-life of Ni-SBA-15 via different mechanistic pathways. CeO2 mitigated Ni poisoning through coke oxidation whereas Cr bolstered the catalyst stability via maintaining a well-defined pore size, structural rigidity, and integrity of the heterogeneous framework, thereby restricting structural collapse, and hence retard sintering of the Ni active sites during the long-term 60 h of continuous reaction. Hydrogen generation from renewable biomass like glycerol could potentially serve as a sustainable energy source and could substantially help reduce the carbon footprint of the environment 

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5. Confinement Effects on the Magnetic Ionic Liquid 1-Ethyl-3-methylimidazolium Tetrachloroferrate(III)

   https://doi.org/10.3390/molecules27175591  

   Burba, Christopher M.; Chang, Hai-Chou (September 2022, Molecules)

   Confinement effects for the magnetoresponsive ionic liquid 1-ethyl-3-methylimidazolium tetrachloroferrate(III), [C2mim]FeCl4, are explored from thermal, spectroscopic, and magnetic points of view. Placing the ionic liquid inside SBA-15 mesoporous silica produces a significant impact on the material’s response to temperature, pressure, and magnetic fields. Isobaric thermal experiments show melting point reductions that depend on the pore diameter of the mesopores. The confinement-induced reductions in phase transition temperature follow the Gibbs–Thomson equation if a 1.60 nm non-freezable interfacial layer is postulated to exist along the pore wall. Isothermal pressure-dependent infrared spectroscopy reveals a similar modification to phase transition pressures, with the confined ionic liquid requiring higher pressures to trigger phase transformation than the unconfined system. Confinement also impedes ion transport as activation energies are elevated when the ionic liquid is placed inside the mesopores. Finally, the antiferromagnetic ordering that characterizes unconfined [C2mim]FeCl4 is suppressed when the ionic liquid is confined in 5.39-nm pores. Thus, confinement provides another avenue for manipulating the magnetic properties of this compound. 

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