Induced dipole moments in amorphous ZnCdS catalysts facilitate photocatalytic H2 evolution
Ontology highlight
ABSTRACT:
SUBMITTER: Wang X
PROVIDER: S-EPMC10960824 | biostudies-literature | 2024 Jan
REPOSITORIES: biostudies-literature
Similar Datasets
Project description:We explore the limits of modifying metal work functions with large molecular dipoles by systematically increasing the dipole moment of archetype donor-acceptor molecules in self-assembled monolayers on gold. Contrary to intuition, we find that enhancing the dipoles leads to a reduction of the adsorption-induced change of the work function. Using atomistic simulations, we show that large dipoles imply electronic localization and level shifts that drive the interface into a thermodynamically unstable situation and trigger compensating charge reorganizations working against the molecular dipoles. Under certain circumstances, these are even found to overcompensate the effect that increasing the dipoles has for the work function.
| S-EPMC3805562 | biostudies-literature
Project description:To suppress the aggregation behavior caused by the high surface energy of quantum dots (QDs), ZnCdS QDs were grown in situ on a g-C3N4 support. During the growth process, the QDs tightly adhered to the support surface. The ZnCdS QDs were prepared by low-temperature sulfurization and cation exchange with a zeolitic imidazolate framework precursor under mild conditions. The heterojunction of g-C3N4/ZnCdS-2 (CN/ZCS-2, with a g-C3N4 to ZIF-8 ratio of 2.0) not only showed excellent optical absorption performance, abundant reactive sites, and a close contact interface but also effectively separated the photogenerated electrons and holes, which greatly improved its photocatalytic hydrogen production performance. Under visible light irradiation (wavelength > 420 nm) without a noble metal cocatalyst, the hydrogen evolution rate of the CN/ZCS-2 heterojunction reached 1467.23 μmol g-1 h-1, and the durability and chemical stability were extraordinarily high.
| S-EPMC9043962 | biostudies-literature
Project description:Multireference calculations can provide accurate information of systems with strong correlation, which have increasing importance in the development of new molecules and materials. However, selecting a suitable active space for multireference calculations is nontrivial, and the selection of an unsuitable active space can sometimes lead to results that are not physically meaningful. Active space selection often requires significant human input, and the selection that leads to reasonable results often goes beyond chemical intuition. In this work, we have developed and evaluated two protocols for automated selection of the active space for multireference calculations based on a simple physical observable, the dipole moment, for molecules with nonzero ground-state dipole moments. One protocol is based on the ground-state dipole moment, and the other is based on the excited-state dipole moments. To evaluate the protocols, we constructed a dataset of 1275 active spaces from 25 molecules, each with 51 active space sizes considered, and have mapped out the relationship between the active space, dipole moments, and vertical excitation energies. We have demonstrated that, within this dataset, our protocols allow one to choose among a number of accessible active spaces one that is likely to give reasonable vertical excitation energies, especially for the first three excitations, with no parameters manually decided by the user. We show that, with large active spaces removed from consideration, the accuracy is similar and the time-to-solution can be reduced by more than 10 fold. We also show that the protocols can be applied to potential energy surface scans and determining the spin states of transition metal oxides.
| S-EPMC10629219 | biostudies-literature
Project description:We demonstrate photocatalytic hydrogen evolution using COF photosensitizers with molecular proton reduction catalysts for the first time. With azine-linked N2-COF photosensitizer, chloro(pyridine)cobaloxime co-catalyst, and TEOA donor, H2 evolution rate of 782 μmol h-1 g-1 and TON of 54.4 has been obtained in a water/acetonitrile mixture. PXRD, solid-state spectroscopy, EM analysis, and quantum-chemical calculations suggest an outer sphere electron transfer from the COF to the co-catalyst which subsequently follows a monometallic pathway of H2 generation from the CoIII-hydride and/or CoII-hydride species.
| S-EPMC5691321 | biostudies-literature
Project description:The study presents enhancement of photocatalytic hydrogen generation after metal-organic framework (MOF5) carbonization at 700 °C and its utilization as a co-catalyst of graphitic carbon nitride (gCN). Thermal treatment of MOF5 affected the formation of ZnO nanoparticles which played the role of co-catalyst for H2 evolution. Moreover, significant band-gap narrowing of MOF5 was observed, which also affected the narrowing of the hybrid band gap. The appropriate conduction band position of the carbonized MOF allowed photogenerated electron transfer from gCN to the carbonized MOF, hence, improving the separation of the charge carriers and reducing the overpotential for H2 generation. The mechanism of the photocatalytic process was also discussed.
| S-EPMC9048713 | biostudies-literature
Project description:An Internet server at http://bip.weizmann.ac.il/dipol calculates the net charge, dipole moment and mean radius of any 3D protein structure or its constituent peptide chains, and displays the dipole vector superimposed on a ribbon backbone of the protein. The server can also display the angle between the dipole and a selected list of amino acid residues in the protein. When the net charges and dipole moments of approximately 12 000 non-homologous PDB biological units (PISCES set), and their unique chains of length 50 residues or longer, were examined, the great majority of both charges and dipoles fell into a very narrow range of values, with long extended tails containing a few extreme outliers. In general, there is no obvious relation between a protein's charge or dipole moment and its structure or function, so that its electrostatic properties are highly specific to the particular protein, except that the majority of chains with very large positive charges or dipoles bind to ribosomes or interact with nucleic acids.
| S-EPMC1933167 | biostudies-literature
Project description:We report here the direct evidence of the existence of a permanent electric dipole moment in both crystal phases of a fullerene-based magnet--the ferromagnetic α-phase and the antiferromagnetic α'-phase of tetra-kis-(dimethylamino)-ethylene-C60 (TDAE-C60)--as determined by dielectric measurements. We propose that the permanent electric dipole originates from the pairing of a TDAE molecule with surrounding C60 molecules. The two polymorphs exhibit clear differences in their dielectric responses at room temperature and during the freezing process with dynamically fluctuating electric dipole moments, although no difference in their room-temperature structures has been previously observed. This result implies that two polymorphs have different local environment around the molecules. In particular, the ferromagnetism of the α-phase is founded on the homogeneous molecule displacement and orientational ordering. The formation of the different phases with respect to the different rotational states in the Jahn-Teller distorted C60s is also discussed.
| S-EPMC4168275 | biostudies-literature
Project description:In this work, an MoS x /g-C3N4 composite photocatalyst was successfully fabricated by a sonochemical approach, where amorphous MoS x was synthesized using a hydrothermal method with Na2MoO4·H2O, H4SiO4(W3O9)4 and CH3CSNH2 as precursors, and g-C3N4 nanosheets were produced using a two-step thermal polycondensation method. The hydrogen-evolution performance of the MoS x /g-C3N4 composite was tested under visible light. The results show that the H2-evolution rate of the MoS x /g-C3N4 (7 wt%) photocatalyst reaches a maximum value of 1586 μmol g-1 h-1, which is about 70 times that of pure g-C3N4 nanosheets. The main reason is that amorphous MoS x forms intimate heterojunctions with g-C3N4 nanosheets, and the introduction of MoS x into g-C3N4 nanosheets not only enhances the ability to convert H+ into H2, but also promotes the separation of photoinduced electron-hole pairs for the photocatalyst. BET analysis shows that the specific surface area and pore volume of g-C3N4 are decreased in the presence of MoS x . XPS analysis manifests that MoS x provides a number of active sites. Mott-Schottky plots show that the conduction band of MoS x (-0.18 V vs. E Ag/AgCl, pH = 7) is more negative than that of g-C3N4 nanosheets.
| S-EPMC9064302 | biostudies-literature
Project description:A simple and computationally feasible procedure for the calculation of net charges and dipole moments of proteins at arbitrary pH and salt conditions is described. The method is intended to provide data that may be compared to the results of transient electric dichroism experiments on protein solutions. The procedure consists of three major steps: (i) calculation of self energies and interaction energies for ionizable groups in the protein by using the finite-difference Poisson-Boltzmann method, (ii) determination of the position of the center of diffusion (to which the calculated dipole moment refers) and the extinction coefficient tensor for the protein, and (iii) generation of the equilibrium distribution of protonation states of the protein by a Monte Carlo procedure, from which mean and root-mean-square dipole moments and optical anisotropies are calculated. The procedure is applied to 12 proteins. It is shown that it gives hydrodynamic and electrical parameters for proteins in good agreement with experimental data.
| S-EPMC1236364 | biostudies-other
Project description:The accuracies of the excited-state dipole and quadrupole moments obtained by TD-DFT are assessed by considering 16 different exchange-correlation functionals and more than 30 medium and large molecules. Except for excited-state presenting a significant charge-transfer character, a relatively limited dependency on the nature of the functional is found. It also turns out that while DFT ground-state dipole moments tend to be too large, the reverse trend is obtained for their excited-state counterparts, at least when hybrid functionals are used. Consequently, the TD-DFT excess dipole moments are often too small, an error that can be fortuitously corrected for charge-transfer transition by selecting a pure or a hybrid functional containing a small share of exact exchange. This error-cancelation phenomena explains the contradictory conclusions obtained in previous investigations. Overall, the largest correlation between CC2 and TD-DFT excess dipoles is obtained with M06-2X, but at the price of a nearly systematic underestimation of this property by ca. 1 D. For the excess quadrupole moments, the average errors are of the order of 0.2-0.6 D·Å for the set of small aromatic systems treated.
| S-EPMC4980690 | biostudies-literature