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1. Identifying Catalytic Active Sites of Trimolybdenum Phosphide (Mo 3 P) for Electrochemical Hydrogen Evolution

   https://doi.org/10.1002/aenm.201900516  

   Kondori, Alireza ; Esmaeilirad, Mohammadreza ; Baskin, Artem ; Song, Boao ; Wei, Jialiang ; Chen, Wei ; Segre, Carlo U. ; Shahbazian‐Yassar, Reza ; Prendergast, David ; Asadi, Mohammad ( May 2019 , Advanced Energy Materials)

   Solid‐state electrocatalysis plays a crucial role in the development of renewable energy to reshape current and future energy needs. However, finding an inexpensive and highly active catalyst to replace precious metals remains a big challenge for this technology. Here, tri‐molybdenum phosphide (Mo₃P) is found as a promising nonprecious metal and earth‐abundant candidate with outstanding catalytic properties that can be used for electrocatalytic processes. The catalytic performance of Mo₃P nanoparticles is tested in the hydrogen evolution reaction (HER). The results indicate an onset potential of as low as 21 mV, H₂formation rate, and exchange current density of 214.7 µmol s⁻¹g⁻¹_cat(at only 100 mV overpotential) and 279.07 µA cm⁻², respectively, which are among the closest values yet observed to platinum. Combined atomic‐scale characterizations and computational studies confirm that high density of molybdenum (Mo) active sites at the surface with superior intrinsic electronic properties are mainly responsible for the remarkable HER performance. The density functional theory calculation results also confirm that the exceptional performance of Mo₃P is due to neutral Gibbs free energy (ΔG_H*) of the hydrogen (H) adsorption at above 1/2 monolayer (ML) coverage of the (110) surface, exceeding the performance of existing non‐noble metal catalysts for HER.

    

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2. Metal‐Organic Framework MIL‐125 Derived Mg 2+ ‐Doped Mesoporous TiO 2 for Photocatalytic CO 2 Reduction

   https://doi.org/10.1002/cptc.202000181  

   Feng, Xuhui ; Pan, Fuping ; Zhang, Peng ; Wang, Xiao ; Zhou, Hong‐Cai ; Huang, Yongheng ; Li, Ying ( October 2020 , ChemPhotoChem)

   In this study, Mg²⁺‐doped mesoporous TiO₂photocatalysts derived from Mg²⁺adsorption (MA) process on MIL‐125, a metal‐organic framework material, were prepared and employed for photocatalytic reduction of CO₂to produce CO. The Mg²⁺doping concentration was controlled by varying the Mg²⁺concentration in the Mg²⁺adsorption process. It was demonstrated that the Mg²⁺doping promoted the generation of surface Ti³⁺and significantly increased transient photocurrent density. Over a 4 h UV/Vis irradiation period, the best performing photocatalyst, 1MA, delivered a CO production rate ∼20 times higher than that of P25, a commercially available TiO₂nanopowder. It is believed that the Mg²⁺adsorption process introduced more favorable properties to the TiO₂photocatalysts, such as higher surface area and porosity for more reactive sites, and concentrated surface Ti³⁺centers for improved charge transfer.

    

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3. Ni 2 P‐Modified Ta 3 N 5 and TaON for Photocatalytic Nitrate Reduction

   https://doi.org/10.1002/cnma.202000174  

   Wei, Lin ; Adamson, Marquix A. S. ; Vela, Javier ( May 2020 , ChemNanoMat)

   Self‐sustaining photocatalytic NO₃⁻reduction systems could become ideal NO₃⁻removal methods. Developing an efficient, highly active photocatalyst is the key to the photocatalytic reduction of NO₃⁻. In this work, we present the synthesis of Ni₂P‐modified Ta₃N₅(Ni₂P/Ta₃N₅), TaON (Ni₂P/TaON), and TiO₂(Ni₂P/TiO₂). Starting with a 2 mM (28 g/mL NO₃⁻−N) aqueous solution of NO₃⁻, as made Ni₂P/Ta₃N₅and Ni₂P/TaON display as high as 79% and 61% NO₃⁻conversion under 419 nm light within 12 h, which correspond to reaction rates per gram of 196 μmol g⁻¹ h⁻¹and 153 μmol g⁻¹ h⁻¹, respectively, and apparent quantum yields of 3–4%. Compared to 24% NO₃⁻conversion in Ni₂P/TiO₂, Ni₂P/Ta₃N₅and Ni₂P/TaON exhibit higher activities due to the visible light active semiconductor (SC) substrates Ta₃N₅and TaON. We also discuss two possible electron migration pathways in Ni₂P/semiconductor heterostructures. Our experimental results suggest one dominant electron migration pathway in these materials, namely: Photo‐generated electrons migrate from the semiconductor to co‐catalyst Ni₂P, and upshift its Fermi level. The higher Fermi level provides greater driving force and allows NO₃⁻reduction to occur on the Ni₂P surface.

    

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4. Resolved Measurements of the CO-to-H 2 Conversion Factor in 37 Nearby Galaxies

   https://doi.org/10.3847/1538-4357/ad23ed  

   Chiang 江, I-Da 宜達 ; Sandstrom, Karin M. ; Chastenet, Jérémy ; Bolatto, Alberto D. ; Koch, Eric W. ; Leroy, Adam K. ; Sun 孙, Jiayi 嘉懿 ; Teng, Yu-Hsuan ; Williams, Thomas G. ( March 2024 , The Astrophysical Journal)

   We measure the CO-to-H₂conversion factor (α_CO) in 37 galaxies at 2 kpc resolution, using the dust surface density inferred from far-infrared emission as a tracer of the gas surface density and assuming a constant dust-to-metal ratio. In total, we have ∼790 and ∼610 independent measurements ofα_COfor CO (2–1) and (1–0), respectively. The mean values forα_{CO (2–1)}andα_{CO (1–0)}are${9.3}_{-5.4}^{+4.6}$and${4.2}_{-2.0}^{+1.9}{M}_{\odot }{\mathrm{pc}}^{-2}{(\mathrm{K}\mathrm{km}{\mathrm{s}}^{-1})}^{-1}$, respectively. The CO-intensity-weighted mean is 5.69 forα_{CO (2–1)}and 3.33 forα_{CO (1–0)}. We examine howα_COscales with several physical quantities, e.g., the star formation rate (SFR), stellar mass, and dust-mass-weighted average interstellar radiation field strength ($\overline{U}$). Among them,$\overline{U}$, Σ_SFR, and the integrated CO intensity (W_CO) have the strongest anticorrelation with spatially resolvedα_CO. We provide linear regression results toα_COfor all quantities tested. At galaxy-integrated scales, we observe significant correlations betweenα_COandW_CO, metallicity,$\overline{U}$, and Σ_SFR. We also find thatα_COin each galaxy decreases with the stellar mass surface density (Σ_⋆) in high-surface-density regions (Σ_⋆≥ 100M_⊙pc⁻²), following the power-law relations${\alpha }_{\mathrm{CO}(2–1)}\propto {\mathrm{\Sigma }}_{\star }^{-0.5}$and${\alpha }_{\mathrm{CO}(1–0)}\propto {\mathrm{\Sigma }}_{\star }^{-0.2}$. The power-law index is insensitive to the assumed dust-to-metal ratio. We interpret the decrease inα_COwith increasing Σ_⋆as a result of higher velocity dispersion compared to isolated, self-gravitating clouds due to the additional gravitational force from stellar sources, which leads to the reduction inα_CO. The decrease inα_COat high Σ_⋆is important for accurately assessing molecular gas content and star formation efficiency in the centers of galaxies, which bridge “Milky Way–like” to “starburst-like” conversion factors.

    

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5. Organo‐Functionalized Lacunary Double Cubane‐Type Oxometallates: Synthesis, Structure, and Properties of [(M II Cl) 2 (V IV O) 2 {((HOCH 2 CH 2 )(H)N(CH 2 CH 2 O))(HN(CH 2 CH 2 O) 2 )} 2 ] (M=Co, Zn)

   https://doi.org/10.1002/chem.202301389  

   Shuaib, Damola T. ; Swenson, LaSalle ; Kaduk, James A. ; Chang, Tieyan ; Chen, Yu‐Sheng ; McNeely, James ; Khan, M. Ishaque ( October 2023 , Chemistry – A European Journal)

   Organofunctionalized tetranuclear clusters [(M^IICl)₂(V^IVO)₂{((HOCH₂CH₂)(H)N(CH₂CH₂O))(HN(CH₂CH₂O)₂)}₂] (1, M=Co,2: M=Zn) containing an unprecedented oxometallacyclic {M₂V₂Cl₂N₄O₈} (M=Co, Zn) framework have been prepared by solvothermal reactions. The new oxo‐alkoxide compounds were fully characterized by spectroscopic methods, magnetic susceptibility measurement, DFT and ab initio computational methods, and complete single‐crystal X‐ray diffraction structure analysis. The isostructural clusters are formed of edge‐sharing octahedral {VO₅N} and trigonal bipyramidal {MO₃NCl} units. Diethanolamine ligates the bimetallic lacunary double cubane core of1and2in an unusual two‐mode fashion, unobserved previously. In the crystalline state, the clusters of1and2are joined by hydrogen bonds to form a three‐dimensional network structure. Magnetic susceptibility data indicate weakly antiferromagnetic interactions between the vanadium centers [J_iso(V^IV−V^IV)=−5.4(1); −3.9(2) cm⁻¹], and inequivalent antiferromagnetic interactions between the cobalt and vanadium centers [J_iso(V^IV−Co^II)=−12.6 and −7.5 cm⁻¹] contained in1.

    

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