摘要：In this work, the intra-EDA method, which is a recently developed energy decomposition analysis scheme for intramolecular non-covalent interaction is extended from gas phase to solvated environment. It is the first analysis scheme that performs analysis for intramolecular interaction in solution. By fragmentation scheme, a molecule is divided into intramolecular interacting fragments and environmental fragments via single bond homolysis breaking. The solvent effect is taken into account by implicit solvation model. Intramolecular interaction free energy is estimated as the separated treatment of inter-fragment interactions in dielectric environment. The analysis results highlight the importance of solvent effects to intramolecular non-covalent interaction.

摘要：Hydrogen production by photoelectrochemical(PEC) water splitting converts the inexhaustible supply of solar radiation to storable H2 as clean energy and thus has received widespread *** efficiency of PEC water splitting is largely determined by the properties of the ***-dimensional(2 D) layered transition metal dichalcogenides(TMDs) are promising candidates for photoelectrodes due to their atomic layer thickness,tunable bandgap,large specific surface area,and high carrier ***,the construction of 2 D TMDs heterostructures provides freedom in material design,which facilitates the further improvement of PEC water *** review begins by describing the mechanism of PEC water splitting and the advantages of 2 D TMDbased heterostructures for photo ***,the design considerations of the heterostructures for enhanced PEC efficiency are comprehensively reviewed with a focus on material selection,band engineering,surface modification,and long-term ***,current challenges and future perspectives for the development of photoelectrodes based on 2 D TMDs heterostructures are addressed.

摘要：In this paper, we reported a solvothermal method for the synthesis of octahedral Pt-Cu bimetallic alloy nanocrystals （NCs） with tunable composition. Inspired by the result from our previous exploration on octahedral Pt-Cu alloy NCs that Cu contents can be tuned from 10 % to 50 %, we further tuned the Cu portion from 50 % to 75 % by simply introducing n-butylamine in the reaction system. It is believed that n-butylamine plays a key role in breaking through a thermodynamic constraint in the formation of Pt-Cu alloy nanocrystals （NCs）. The synergistic effect of underpotential deposition-like Cu reduction and the different complexion abilities of amine group of n-butylamine with two metal species effectively tuned the reduction kinetics, by which each reduced Pt atom is able to catalyze reduction of more Cu atoms and be fully covered with 12 Cu atoms in the Pt-Cu alloy crystal, while Cu precursor is not able to be reduced solely and bind solely with Cu atoms, resulting in the successful tuning of Cu composition from 50 % to 75 %. In addition, we investigated the electro-catalytic activity of Pt-Cu bimetallic alloy NCs with different composition in electro-oxidation of methanol. The as-prepared PtCu3 NCs exhibit excellent electro-catalytic performance and stability in comparison with commercial Pt black and other compositional Pt-Cu alloy NCs.

摘要：The photo-induced ultrafast electron dynamics in both anatase and rutile TiO_(2) are investigated by using the Boltzmann transport equation with the explicit incorporation of electron-phonon scattering *** structural parameters required for dynamic simulations are obtained from ab initio *** results show that although the longitudinal optical modes significantly affect the electron energy relaxation dynamics in both phases due to strong Fr?hlich-type couplings,the detailed relaxation mechanisms have obvious *** the case of a single band,the energy relaxation time in anatase is 24.0 fs,twice longer than 11.8 fs in *** discrepancy is explained by the different diffusion distributions over the electronic Bloch states and different scattering contributions from acoustic modes in the two *** for the multiple-band situation involving the lowest six conduction bands,the predicted overall relaxation times are about 47 fs and 57 fs in anatase and rutile,respectively,very different from the case of the single *** slower relaxation in rutile is attributed to the existence of multiple rate-controlled steps during the dynamic *** present findings may be helpful to control the electron dynamics for designing efficient TiO_(2)-based devices.

摘要：Electrochemical energy conversion technologies involving processes such as water splitting and O_(2)/CO_(2) reduction,provide promising solutions for addressing global energy scarcity and minimizing adverse environmental ***,due to a lack of an in-depth understanding of the reaction mechanisms and the nature of the active sites,further advancement of these techniques has been limited by the development of efficient and robust ***,in situ characterization of these electrocatalytic processes under working conditions is *** this review,recent applications of in situ Raman spectroscopy and X-ray absorption spectroscopy for various nano-and single-atom catalysts in energy-related reactions are *** cases are highlighted,including the capture of oxygen-containing intermediate species formed during the reduction of oxygen and oxidation of hydrogen,and the detection of catalyst structural transformations occurring with the change in potential during the evolution of oxygen and reduction of CO_(2).Finally,the challenges and outlook for advancing in situ spectroscopic technologies to gain a deeper fundamental understanding of these energy-related electrocatalytic processes are discussed.

摘要：Selective hydrodeoxygenation of lignin derivatives into aromatic compounds is a promising route for the upgrading of lignin *** carbide catalysts have exhibited excellent selectivity in hydrodeoxygenation reactions,while their structure-activity relationship is still in ***,a liquid-phase atomic layer deposition method was employed to synthesize W_(2)C/SiO_(2) catalysts with uniform and size-controllable W_(2)C *** gas-phase hydrodeoxygenation of lignin-derived m-cresol at 350℃,these W_(2)C/SiO_(2) catalysts showed superior toluene selectivities(>95%)regardless of the W_(2)C particle *** optimal W_(2)C particle size of~7 nm was obtained for achieving the highest W_(2)C-based hydrodeoxygenation *** contrast,the turnover rate per surface W site increased almost monotonously as the W_(2)C particle size increased within 0.7-15 nm,attributable to high-index planes appeared on the larger W_(2)C *** effects of m-cresol and H_(2),taken together with temperature-programmed desorption of probe molecules and theoretical treatments,further indicate that the W_(2)C surface is nearly saturated by adsorbed m-cresol or its derivates under the reaction condition and the H-addition of the C7H7*intermediate to form toluene,instead of the initial C-O cleavage in m-cresol,acts as the rate-determining step.A side-by-side comparison between W_(2)C(102)and W_(2)C(001)catalyst surfaces in theoretical simulations of m-cresol hydrodeoxygenation verifies that high-index planes can stabilize kinetically-relevant transition states more effectively than the low-index ones,as a result of more available less-coordinated active sites on the *** above findings bring new mechanistic insights into the site requirements of supported W_(2)C nanocatalysts,distinct from those metal-catalyzed hydrodeoxygenation of oxygenates.

摘要：Cu-based catalysts are commonly used in industry for methanol *** this study,supported catalysts of 5 wt%Cu/Al_(2)O_(3)and 5 wt%Cu/ZnO were prepared,and their surface characteristics during H_(2) reduction and CO_(2)hydrogenation were investigated using in situ Fourier transform infrared spectroscopy(FTIR),ex situ X-ray photoelectron spectroscopy,and high sensitivity low energy ion scattering *** the H2 reduction and CO_(2)hydrogenation processes,it was found that Al_(2)O_(3)can stabilize Cu^(+).In situ FTIR spectra indicated that the 5 wt%Cu/Al_(2)O_(3)can adsorb large amounts of bicarbonate and carbonate species,which then convert into formate during CO_(2)*** the 5 wt%Cu/ZnO,it was found that Cu nanoparticles were gradually covered by a highly defective ZnOx overlayer during H2 reduction,which can effectively dissociate *** CO_(2)hydrogenation,the adsorbed bicarbonate or carbonate species can convert into formate and then into a methoxy *** these surface sensitive methods,a more in-depth understanding of the synergistic effect among the Cu,Al_(2)O_(3),and ZnO components of Cu-based catalysts was achieved.

摘要：Recent studies confirm that the emerging bifunctional catalysts consisting of metal oxide and zeolites can directly convert syngas into high-quality gasoline,however,the formation mechanism of iso-paraffins and the difference with the conventional FT/zeolite catalyst have not been ***,three one-dimensional SAPO zeolites with diverse micropore sizes were synthesized and assembled with ZnAlO_(x)with spinel *** was found that ZnAlO_(x)/SAPO-41 and ZnAlO_(x)/SAPO-11 with medium micropore sizes favored the formation of C_(5)–C_(11)hydrocarbons with a high content of *** characterizations pointed out that the formation of iso-paraffins over SAPO-11 followed a pore-mouth catalysis mechanism,which means the isomerization of linear hydrocarbons can only take place near the pore mouth region of *** mechanism only allows the formation of mono-branched iso-paraffins in the C_(5)–C_(11)range,which are less prone to be cracked than their di-branched isomers.A careful comparative analysis between ZnAlO_(x)/SAPO-11 and Co/H-meso-ZSM-5 was also made in terms of product distribution,activity,and stability.

摘要：The synthesis of nanocrystals(NCs)with defined morphology and surface structure provides an effective way to investigate the structure-activity relationship of nanocatalytsts,and it will facilitate the design of nanocatalysts with excellent catalytic *** this paper,we developed a facile method to synthesize PdH0.43 NCs with the shape of cube,octahedron and rhombic dodecahedron(RD),whose surface facets are{100},{111}and{110},*** asprepared PdH0.43 NCs are highly stable and exhibit enhanced catalytic activity and extremely low overpotential towards electro-oxidation of formic acid compared with the commercial Pd black and three types of Pd *** specific activity of the cubic PdH0.43 NCs is more than five times that of the commercial Pd black and two times that of the cubic Pd *** the three types of PdH0.43 NCs with different surface structure,the activity order is followed by PdH0.43{100}>PdH0.43{111}>PdH0.43{110}.

摘要：Noble metal-reducible oxide interfaces have been regarded as one of the most active sites for water-gas shift ***,the molecular reaction mechanism of water-gas shift reaction at these interfaces still remains ***,water-gas shift reaction at Pt-NiO interfaces has been in-situ explored using surface-enhanced Raman spectroscopy by construction of Au@Pt@NiO *** Raman spectroscopic evidence demonstrates that water-gas shift reaction at Pt-NiO interfaces proceeds via an associative mechanism with the carbonate species as a key *** carbonate species is generated through the reaction of adsorbed CO with gaseous water,and its decomposition is a slow step in water-gas shift ***,the Pt-NiO interfaces would promote the formation of this carbonate intermediate,thus leading to a higher activity compared with pure *** spectral information deepens the fundamental understanding of the reaction mechanism of water-gas shift reaction,which would promote the design of more efficient catalysts.