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Abstract: In this paper, TS-1 powder was prepared by utilizing pretreated titanium dioxide as titanium source. The structure and activity of the prepared catalysts were investigated by XRD, FT-IR, UV–vis and semicontinuous reaction of cyclohexanone ammoximation. The results showed that the prepared catalyst with pretreated titanium dioxide as a titanium source containing less Brönsted acidic sites than that of the standard sample using TBOT as titanium source. After the post-treatment by 0.5M hydrochloric acid aqueous solution for removing the extra-framework Ti species, the obtained catalysts displayed almost the same catalytic activity under optimal condition as the titanium source of TBOT. [Copyright &y& Elsevier]

• The reaction mechanisms of each step evolve with the surface Cl/Cu ratios. • The origin of the K effect was explored by Van-der-Waals corrected DFT calculations. • Free energy analysis is consistent with the experimental observation. • KCl modifies the electronic structure of the surface. Potassium promoters are widely used in industrial catalysts of ethylene oxychlorination to achieve optimum performance. However, the origin of the promoter effect is not fully understood. Herein, we investigated the potassium promotion effect on CuCl 2 /γ-Al 2 O 3 catalyzed ethylene oxychlorination by kinetic experiments and DFT calculations. Kinetic experiments observed the effect of KCl on individual steps, and the evolution of the reaction mechanisms with Cl/Cu ratios. Further exploration via DFT found that KCl increases the formation energy of Cl vacancy (Δ E v) and thus inhibits the reduction activity, which is attributed to the shift-down of Bader charge of Cl. Δ E v boosts with the decline of Cl/Cu ratios; thus, ethylene can extract Cl atoms from the surface with a Cl/Cu ratio of 2, while it anchors to metal atoms at lower Cl/Cu ratios. The distinct adsorption modes reflect the evolution of reaction mechanisms with Cl/Cu ratios. KCl facilitates the adsorption of oxygen owing to the shift-up of the Bader charge of Cu atom. Potassium reduces the Gibbs free energy barrier of the oxidation step, which agrees with the experimental observation. It is concluded that the potassium promoter effect on the catalytic performance mainly results from the modification of the charge of surface atoms. [ABSTRACT FROM AUTHOR]

[Display omitted] • Using UV–vis-NIR to analyze the kinetics of ethylene oxychlorination. • Co-promoter effect of alkali and alkali earth metals on ethylene oxychlorination. • Methods to design and predict the reaction rate and Cu2+ concentration for the steady-state. The comprehensive kinetic study for CuCl 2 /γ-Al 2 O 3 -based catalysts was performed to elucidate the co-promoter effect in the ethylene oxychlorination, one of the most significant industrial processes to produce vinyl chloride monomer. Kinetic analysis was performed separately by transient kinetic studies, taking account of the reduction and oxidation steps in the catalytic cycle. The promoter effects on ethylene oxychlorination were ascribed to their influence on the Cu2+ reduction or Cu+ oxidation in the catalytic cycle. The reaction rate-diagram was gained and used to predict the steady-state reaction rate and Cu oxidation state by an operando setup combing MS and UV–vis-NIR spectroscopy. The results indicated that the K-doped catalyst could greatly increase the reaction rate of the oxidation step, which gave rise to higher Cu2+ concentration on the catalyst. Mg-doped catalyst had a great effect on enhancing the reaction rate for the reduction step. K and Mg co-doped catalyst had the dual effect, both the reaction rate and Cu oxidation state were located between K and Mg mono-doped catalyst. The results of steady-state reactions indicated that the reaction rates were quite close with that predicated by the rate-diagram. Byproduct analysis during the steady-state was also performed, the results demonstrated that the co-promoted catalysts can also reduce the byproduct formation. The current study is expected to provide one way for exploring the potential benefits of co-promotion on CuCl 2 /γ-Al 2 O 3 -based industrial oxychlorination catalysts to improve the catalytic performance and understand the reaction further. [ABSTRACT FROM AUTHOR]

• Cofed C 2 H 4 hydrogenated faster than CO, and mainly produced ethane and higher olefins. • Cofed C 2 H 4 followed a similar reaction mechanism as Fischer-Tropsch synthesis. • Cofed C 2 H 4 enhanced chain growth probability and increased C 3+ O/P ratio. • Hydrocracking of cofed C 2 H 4 formed C 1 monomer and the C 1 monomer got further incorporated into the growing chain. Understanding the secondary reactions of olefins in Fischer Tropsch Synthesis (FTS) is crucial for enhancing olefin selectivity in Fischer Tropsch to Olefin (FTO) reaction. Equimolar ethene towards CO was used as a probe to be cofed into the syngas (H 2 : CO = 2) to study the effect on the product distribution over cobalt-based catalysts supported on γ-alumina, α-alumina and carbon nanotube (CNT), respectively. The experiments were performed at T = 210 °C; P tot = 1.85 bar, P CO = 0.11 bar; P H2 = 0.22 bar; P C2H4 = 0 or 0.11 bar with Ar as the balance. On all three catalysts, ethene co-feeding at this concentration inhibited CO conversion and the products were mainly from ethene. The products showed similar Anderson-Schulz-Flory (ASF) distribution as typical for FTS products. Ethene co-feeding can both enhance the chain growth probability and significantly increase the O/P ratio of C 3 -C 6 hydrocarbons. An isotopic switch from 12CO/H 2 /Ar→13CO/H 2 /C 2 H 4 /Kr proved that ethene can hydrocrack to C 1 intermediates and be incorporated into the growing chain. On the other hand, the hydrogenation activity can be significantly suppressed due to the H 2 scavenging effect and possibly competitive adsorption with H 2. [ABSTRACT FROM AUTHOR]

In this contribution, we combine density functional theory (DFT) calculations, experimental kinetic study and DFT-assisted analysis to elucidate the impact of the interface of monolayer Pt on the Ni surface on catalytic performance of steam methane reforming including carbon formation on core-shell (Ni@Pt) catalysts and compare it with Ni and Pt catalysts. We demonstrate that core-shell structured Ni@Pt significantly lowers the carbon formation without sacrificing much the activity. The DFT results demonstrate that the metal identity, core shell structure and support have significant impacts on the reaction mechanisms. The direct methane activation is energetically favorable reaction pathway on Ni, while the OH* assisted methane activation is the favorable pathway on Pt and Ni@Pt catalysts, where methane activation is the rate-determining step on all catalysts. We unambiguously reveal that the core-shell Ni@Pt catalyst modified the surface Pt electron density and shifted d -band center away from Fermi level compared to Ni(1 1 1) and Pt(1 1 1). It results in a strong basic surface OH* which actively reacts with CH x and thus enhances carbon formation resistance. Above all, Ni-core/Pt-shell particle could decouple the activity and carbon resistance to keep the activity and reduce carbon formation simultaneously in methane steam reforming. In addition, by taking into account the activation of steam on the support, the effective activation energy estimated from DFT-assisted analysis is well consistent with the experimental value on the both Ni and Ni@Pt catalysts, which could shed some light on building a bridge between experimental work and DFT-assisted kinetic study. [ABSTRACT FROM AUTHOR]

• Small Ni particles exhibit higher steam methane reforming activity than large ones. • The size-dependent activity of Ni catalysts is related to the surface-dependent activity. • Ni(2 1 1) is the most active surface for steam methane reforming. • Decreased Ni(2 1 1) surface fraction results in reduced Ni activity as size increases. Fundamental understanding of the size-dependent activity is essential to harness powers of the nanocatalysts. Here we report an experimental and theoretical study of the Ni particle size effect on activity of steam methane reforming (SMR) to achieve a better understanding of the size dependence of kinetic behavior at an atomic level. A kinetic study illustrated the higher forward methane turnover frequency on the smaller sized Ni particles. The size-dependent activity was well reproduced by microkinetic modeling on a truncated octahedron model with the kinetic parameters estimated by the improved unity bond index-quadratic exponential potential (UBI-QEP) and the Brønsted–Evans–Polanyi (BEP) relationship. Microkinetic modeling suggested that the size-dependent activity of Ni catalysts is associated with the surface-dependent activity. Much higher activity of Ni(2 1 1) than Ni(1 1 1) and Ni(1 0 0) accompanied by decreased Ni(2 1 1) surface fraction results in reduced Ni activity as particle size increases. The activity of Ni(1 1 1) is limited by high free energy barriers, while that of Ni(1 0 0) is limited by site blockage by C* and CH*. This work offers a feasible approach to gain insight into size-dependent activity and to aid rational catalyst design for SMR in which preparing extremely small Ni particles (≤6 nm) might be a good strategy. [ABSTRACT FROM AUTHOR]