: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

We developed two-step solution-phase reactions to form hybrid materials of Mn3O4 nanoparticles on reduced graphene oxide (RGO) sheets for lithium ion battery applications. Mn3O4 nanoparticles grown selectively on RGO sheets over free particle growth in solution allowed for the electrically insulating Mn3O4 nanoparticles wired up to a current collector through the underlying conducting graphene network. The Mn3O4 nanoparticles formed on RGO show a high specific capacity up to ~900mAh/g near its theoretical capacity with good rate capability and cycling stability, owing to the intimate interactions between the graphene substrates and the Mn3O4 nanoparticles grown atop. The Mn3O4/RGO hybrid could be a promising candidate material for high-capacity, low-cost, and environmentally friendly anode for lithium ion batteries. Our growth-on-graphene approach should offer a new technique for design and synthesis of battery electrodes based on highly insulating materials.

Mn3O4-Graphene Hybrid as a High Capacity Anode Material for Lithium Ion Batteries

The appropriate interfacial contact of heterojunction photocatalysts plays a critical role in transfer/separation of interfacial charge carriers. Design of two-dimensional (2D)/2D surface-to-surface heterojunction is an effective method for improving photocatalytic activity since greater contact area can enhance interfacial charge transfer rate. Herein, ultrathin 2D/2D WO3/g-C3N4 step-like composite heterojunction photocatalysts were fabricated by electrostatic self-assembly of ultrathin tungsten trioxide (WO3) and graphitic carbon nitride (g-C3N4) nanosheets. The ultrathin WO3 and g-C3N4 nanosheets were obtained by electrostatic-assisted ultrasonic exfoliation of bulk WO3 and a two-step thermal-etching of bulk g-C3N4, respectively. The thickness of ultrathin WO3 and g-C3N4 nanosheets are 2.5–3.5 nm, which is equivalent to 5–8 atomic or molecular layer thickness. This ultrathin layered heterojunction structure can enhance surface photocatalytic rate because photogenerated electrons and holes at heterogeneous interface more easily transfer to surface of photocatalysts. Therefore, the obtained ultrathin 2D/2D WO3/g-C3N4 step-scheme (S-scheme) heterojunction photocatalysts exhibited better H2-production activity than pure g-C3N4 and WO3 with the same loading amount of Pt as cocatalyst. The mechanism and driving force of charge transfer and separation in S-scheme heterojunction photocatalysts are investigated and discussed. This investigation will provide new insight about designing and constructing novel S-scheme heterojunction photocatalysts.

Ultrathin 2D/2D WO3/g-C3N4 step-scheme H2-production photocatalyst

Electrocatalytic transformation of carbon dioxide (CO2) and water into chemical feedstocks offers the potential to reduce carbon emissions by shifting the chemical industry away from fossil fuel dependence. We provide a technoeconomic and carbon emission analysis of possible products, offering targets that would need to be met for economically compelling industrial implementation to be achieved. We also provide a comparison of the projected costs and CO2 emissions across electrocatalytic, biocatalytic, and fossil fuel-derived production of chemical feedstocks. We find that for electrosynthesis to become competitive with fossil fuel-derived feedstocks, electrical-to-chemical conversion efficiencies need to reach at least 60%, and renewable electricity prices need to fall below 4 cents per kilowatt-hour. We discuss the possibility of combining electro- and biocatalytic processes, using sequential upgrading of CO2 as a representative case. We describe the technical challenges and economic barriers to marketable electrosynthesized chemicals.

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What would it take for renewably powered electrosynthesis to displace petrochemical processes

Because of its fundamental importance in many branches of science, hydrogen bonding is a subject of intense contemporary research interest. The physical and chemical properties of hydrogen bonds in the ground state have been widely studied both experimentally and theoretically by chemists, physicists, and biologists. However, hydrogen bonding in the electronic excited state, which plays an important role in many photophysical processes and photochemical reactions, has scarcely been investigated.Upon electronic excitation of hydrogen-bonded systems by light, the hydrogen donor and acceptor molecules must reorganize in the electronic excited state because of the significant charge distribution difference between the different electronic states. The electronic excited-state hydrogen-bonding dynamics, which are predominantly determined by the vibrational motions of the hydrogen donor and acceptor groups, generally occur on ultrafast time scales of hundreds of femtoseconds. As a result, state-of-the-art femtos...

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Hydrogen Bonding in the Electronic Excited State

Enhanced H2O2 production by selective electrochemical reduction of O2 on fluorine-doped hierarchically porous carbon

Electrochemical reduction of CO_2 to ethanol, a clean and renewable liquid fuel with high heating value, is an attractive strategy for global warming mitigation and resource utilization. However, converting CO_2 to ethanol remains great challenge due to the low activity, poor product selectivity and stability of electrocatalysts. Here, the B- and N-co-doped nanodiamond (BND) was reported as an efficient and stable electrode for selective reduction of CO_2 to ethanol. Good ethanol selectivity was achieved on the BND with high Faradaic efficiency of 93.2 % (−1.0 V vs. RHE), which overcame the limitation of low selectivity for multicarbon or high heating value fuels. Its superior performance was mainly originated from the synergistic effect of B and N co-doping, high N content and overpotential for hydrogen evolution. The possible pathway for CO_2 reduction revealed by DFT computation was CO_2→*COOH→*CO→*COCO→*COCH_2OH→*CH_2OCH_2OH→CH_3CH_2OH.

Selective Electrochemical Reduction of Carbon Dioxide to Ethanol on a Boron- and Nitrogen-Co-doped Nanodiamond

Single-atom platinum confined by the interlayer nanospace of carbon nitride for efficient photocatalytic hydrogen evolution

Fabrication of g-C3N4/Ti3C2 composite and its visible-light photocatalytic capability for ciprofloxacin degradation

Construction of Z-Scheme g-C3N4/RGO/WO3 with in situ photoreduced graphene oxide as electron mediator for efficient photocatalytic degradation of ciprofloxacin.

Yan Su

Papers

Enhanced H2O2 production by selective electrochemical reduction of O2 on fluorine-doped hierarchically porous carbon

Selective Electrochemical Reduction of Carbon Dioxide to Ethanol on a Boron- and Nitrogen-Co-doped Nanodiamond

Single-atom platinum confined by the interlayer nanospace of carbon nitride for efficient photocatalytic hydrogen evolution

Fabrication of g-C3N4/Ti3C2 composite and its visible-light photocatalytic capability for ciprofloxacin degradation

Construction of Z-Scheme g-C3N4/RGO/WO3 with in situ photoreduced graphene oxide as electron mediator for efficient photocatalytic degradation of ciprofloxacin.