Density functional theory was employed to study the water−gas shift (WGS) reaction for two structural modelsnamely, a single Au atom and a Au nanorodsupported on the (110) surface of ceria. The carboxyl mechanism involving a COOH intermediate is strongly preferred over the redox mechanism, which would require O− H bond cleavage of ceria-bound hydroxyl groups. Two candidate ratecontrolling elementary reaction steps were identified in the carboxyl mechanism: oxygen vacancy formation and COOH formation from CO and OH adsorbed to Au and the ceria support, respectively. A reaction energy analysis shows that both steps are more favorable on clustered Au atoms than on a single Au atom. CO adsorption on a single Au atom is hindered because of its negative charge. Comparison to literature data shows that the WGS reaction is preferred for a gold cluster on the CeO 2 (110) surface over the CeO 2 (111) one because of the lower binding energy of OH on the former surface. These results are discussed in the light of a large number of experimental and theoretical studies of the Au/CeO 2 catalyzed WGS reaction.

Co 3 O 4 is a well-known catalyst in the oxidation reaction. In such a catalyst, the geometric and electronic structures of tetrahedrally coordinated Co 2+ and octahedrally coordinated Co 3+ can be regulated by directional metal ion substitution strategy, accompanied by the modification of catalytic activity. Herein, normal and inverse cobalt-based spinel catalysts M x Co 3−x O 4 (M = Zn and Ni) with a threedimensionally ordered macroporous (3DOM) structure were successfully fabricated through the carboxy-modified colloidal crystal templating (CMCCT) method. The relationship between the dopant and activity during NO x -assisted soot oxidation was systematically studied by means of XPS, H 2 -TPR, soot-TPR, isothermal anaerobic titrations, NO-TPO, soot-TPO, and so on. The well-defined 3DOM structure for M x Co 3−x O 4 catalysts can improve the contact efficiency of soot and catalysts. 3DOM NiCo 2 O 4 exhibits high catalytic activity for soot oxidation under a loose contact mode between soot and catalyst. For instance, its T 50 and TOF values are 379 °C and 1.36 × 10 −3 s −1 , respectively. The doping of Ni to Co 3 O 4 will induce the structural distortion, improve the density of oxygen vacancies, and enhance lattice oxygen mobility. It leads to more surface-active oxygen species. A vacancy-mediated pathway of NO oxidation on the spinel catalyst is proposed according to the experimental results of in situ DRIFT spectra, in situ Raman spectra, and the theoretical knowledge of coordination chemistry of metal−NO. The catalytic performance of soot oxidation is highly related to the capacity of a catalyst in oxidizing NO to NO 2 . Therefore, indirect NO 2 -assisted mechanism is proposed for soot oxidation under an NO/O 2 /N 2 atmosphere.

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Initial reaction mechanisms of lignin pyrolysis were studied by large-scale ReaxFF molecular dynamics simulations (ReaxFF MD) facilitated by the first GPU-enabled code (GMD-Reax) and the unique reaction analysis tool (VARxMD). Simulations were performed over wide temperature ranges both for heat up at 300–2100 K and for NVT at 500–2100 K with a large lignin model, which contained 15920 atoms and was constructed based on Adler’s softwood lignin model. By utilizing the relatively continuous observation for pyrolysate evolution in slow heat up simulations, three stages for lignin pyrolysis are proposed by pyrolysate fractions. The underlying mechanisms for the three stages are revealed by analyzing the species structure evolution and the reactions of linkages, aryl units, propyl chains, and methoxy substituents. Stage I is characterized with the complete decomposition of source lignin molecules at low temperatures dominated by breaking of α-O-4 and β-O-4 linkages. The temperature in stage II is relatively high where cracking of all the linkages occurs, accompanied by conversion of propyl chains and methoxy substituents. Stage III mapping to high temperature shows the formation of heavy pyrolysates by recombination reactions of five-, six-, or seven-membered aliphatic rings. The heterocyclic oxygen-containing rings are revealed as important intermediates for the aryl monomer ring opening into aliphatic rings of five-membered, seven-membered, or even larger. The pathways for small molecule formation observed in this work are broadly in agreement with the literature. This work demonstrates a new methodology for investigating the overall behaviors and the underlying complex mechanisms of lignin pyrolysis.