Simplification of solvation shell with water clusters in the simulation of electrochemical nitrogen reduction reaction.

Electrochemical methods for nitrogen reduction have received extensive attention due to the mild reaction conditions. In order to gain an insight into the mechanism of the electrochemical nitrogen reduction process, theoretical simulations are necessary. However, current simulation studies contain many imprecise approximations that may hinder the real recognition of the reaction process.

Theoretical Perspective on the Design of Surface Frustrated Lewis Pairs for Small-Molecule Activation.

The excellent reactivity of frustrated Lewis pairs (FLP) to activate small molecules has gained increasing attention in recent decades. Though the development of surface FLP (SFLP) is prompting the application of FLP in the chemical industry, the design of SFLP with superior activity, high density, and excellent stability for small-molecule activation is still challenging. Herein, we review the progress of designing SFLP by surface engineering, screening natural SFLP, and the dynamic formation of SFLP from theoretical perspectives.

Finding Natural, Dense, and Stable Frustrated Lewis Pairs on Wurtzite Crystal Surfaces for Small-Molecule Activation.

The surface frustrated Lewis pairs (SFLPs) open up new opportunities for substituting noble metals in the activation and conversion of stable molecules. However, the applications of SFLPs on a larger scale are impeded by the complex construction process, low surface density, and sensitivity to the reaction environment. Herein, wurtzite-structured crystals such as GaN, ZnO, and AlP are found for developing natural, dense, and stable SFLPs.

Metal-Oxo Electronic Tuning via In Situ CO Decoration for Promoting Methane Conversion to Oxygenates over Single-Atom Catalysts.

Direct methane conversion (DMC) to oxygenates at low temperature is of great value but remains challenging due to the high energy barrier for C-H bond activation. Here, we report that in situ decoration of Pd-ZSM-5 single atom catalyst (SAC) by CO molecules significantly promoted the DMC reaction, giving the highest turnover frequency of 207 h ever reported at room temperature and ~100 % oxygenates selectivity with HO as oxidant. Combined characterizations and DFT calculations illustrate that the C-atom of CO prefers to coordinate with Pd, which donates electrons to the Pd-O active center (L-Pd-O, L=CO) generated by HO oxidation.

α-Alkylation of ketones with primary alcohols by an active non-noble metal Cu/CuOx catalyst.

Development of convenient and effective heterogeneous non-noble metal catalysts for α-alkylation of ketones with alcohols is challenging in heterogeneous catalysis. Here, we report active non-noble metal Cu/CuOx catalysts for the construction of C-C bonds by the α-alkylation of ketones with alcohols through the borrowing hydrogen methodology. The optimal Cu/CuOx-250 catalyst exhibits good catalytic performance in the reactions to give the corresponding products in 50-96% yields.

Simulation and Experimental Study of Solid-Liquid Extraction of Coal Tar Residue Based on Different Extractants.

Coal tar residue (CTR) is recognized as a hazardous industrial waste with a high carbon content and coal tar consisting mainly of toxic polycyclic aromatic hydrocarbons (PAHs). The coal tar in CTR can be deeply processed into high-value-added fuels and chemicals. Effective separation of coal tar and residue in CTR is a high-value-added utilization method for it.

An electron-hole rich dual-site nickel catalyst for efficient photocatalytic overall water splitting.

Photocatalysis offers an attractive strategy to upgrade HO to renewable fuel H. However, current photocatalytic hydrogen production technology often relies on additional sacrificial agents and noble metal cocatalysts, and there are limited photocatalysts possessing overall water splitting performance on their own. Here, we successfully construct an efficient catalytic system to realize overall water splitting, where hole-rich nickel phosphides (NiP) with polymeric carbon-oxygen semiconductor (PCOS) is the site for oxygen generation and electron-rich NiP with nickel sulfide (NiS) serves as the other site for producing H.

Study on the Preparation of Clean Liquid Fuel by Wide Fraction High-Temperature Coal Tar Deep Hydro-Upgrading on a Pilot Plant Trickle Bed Reactor.

High-temperature coal tar contains a high content of heavy components, and the mechanism of its hydrogenation to fuel oil has not been completely revealed at present. In this work, clean environmental friendly fuel oil was obtained from wide fraction high-temperature coal tar (WHTCT) hydrotreated in a three-stage continuous pilot-scale trickle bed reactor filled with commercial catalysts. The effect of reaction temperature (345-405 °C), reaction pressure (10-18 MPa), and LHSV (0.

Perceptions on the treatment of apparent isotope effects during the analyses of reaction rate and mechanism.

Isotope substitution, a fascinating tool of physical chemistry, has been broadly applied in the research field of heterogeneous catalysis. In general, due to the differences in the mass-related atomic vibrational frequencies and zero-point energy of isotopic molecules, the apparent isotope effect (AIE) or observed kinetic isotope effect (observed KIE) from isotope substitution examination could provide unique knowledge regarding the reaction rate and mechanism of a catalytic reaction, such as the rate-determining step, key reaction intermediate, or catalyst design and synthesis. However, the treatment of the AIE is not as straightforward as the isotopic switch experiment, and needs sufficient care and comprehensive identification to deal with the influences from the equilibrium isotope effects (EIEs) of quasi-equilibrium elementary steps, kinetic isotope effect (KIE) of the pseudo rate-determining step, transition states, intrinsic reaction barriers, Fundamentally, the key factors affecting the AIE could be the partition function part and the zero-point energy part of each single elementary step.

Synergy of Pd atoms and oxygen vacancies on InO for methane conversion under visible light.

Methane (CH) oxidation to high value chemicals under mild conditions through photocatalysis is a sustainable and appealing pathway, nevertheless confronting the critical issues regarding both conversion and selectivity. Herein, under visible irradiation (420 nm), the synergy of palladium (Pd) atom cocatalyst and oxygen vacancies (OVs) on InO nanorods enables superior photocatalytic CH activation by O. The optimized catalyst reaches ca.

Single Carbon Vacancy Traps Atomic Platinum for Hydrogen Evolution Catalysis.

The coordinated configuration of atomic platinum (Pt) has always been identified as an active site with high intrinsic activity for hydrogen evolution reaction (HER). Herein, we purposely synthesize single vacancies in a carbon matrix (defective graphene) that can trap atomic Pt to form the Pt-C configuration, which gives exceptionally high reactivity for HER in both acidic and alkaline solutions. The intrinsic activity of Pt-C site is valued with a turnover frequency (TOF) of 26.

Screening silica-confined single-atom catalysts for nonoxidative conversion of methane.

The development of a single-atom iron catalyst (Fe©SiO) for the direct conversion of methane to olefins, aromatics, and hydrogen is a breakthrough in the field of nonoxidative conversion of methane (NCM). However, the optimization of the catalyst remains desirable for industrial applications. Herein, 25 transition metals, including Sc, Ti, V, Cr, Mn, Co, Ni, Cu, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Hf, Ta, W, Re, Os, Ir, Pt, and Au, are selected to replace the central Fe atom for screening out better single-atom catalysts for the NCM.

Unravelling the Enigma of Nonoxidative Conversion of Methane on Iron Single-Atom Catalysts.

The direct, nonoxidative conversion of methane on a silica-confined single-atom iron catalyst is a landmark discovery in catalysis, but the proposed gas-phase reaction mechanism is still open to discussion. Here, we report a surface reaction mechanism by computational modeling and simulations. The activation of methane occurs at the single iron site, whereas the dissociated methyl disfavors desorption into gas phase under the reactive conditions.

Semi-solid and solid frustrated Lewis pair catalysts.

Recently discovered homogeneous frustrated Lewis pairs (FLPs) have attracted much attention for metal-free catalysis due to their promising potential for the activation of small molecules (e.g., H2, CO, CO2, NOx and many others).

Design of N-Coordinated Dual-Metal Sites: A Stable and Active Pt-Free Catalyst for Acidic Oxygen Reduction Reaction.

We develop a host-guest strategy to construct an electrocatalyst with Fe-Co dual sites embedded on N-doped porous carbon and demonstrate its activity for oxygen reduction reaction in acidic electrolyte. Our catalyst exhibits superior oxygen reduction reaction performance, with comparable onset potential (E, 1.06 vs 1.

Solid frustrated-Lewis-pair catalysts constructed by regulations on surface defects of porous nanorods of CeO.

Identification on catalytic sites of heterogeneous catalysts at atomic level is important to understand catalytic mechanism. Surface engineering on defects of metal oxides can construct new active sites and regulate catalytic activity and selectivity. Here we outline the strategy by controlling surface defects of nanoceria to create the solid frustrated Lewis pair (FLP) metal oxide for efficient hydrogenation of alkenes and alkynes.

Step-Edge Assisted Direct Linear Alkane Coupling.

Direct coupling of alkanes via C-H activation of terminal methyl groups has acquired tremendous interests both scientifically and technically. Herein we present the results of linear alkane-coupling at the step edges of Cu surfaces at modulated temperatures. Combining the observations of scanning tunneling microscopy (STM) with density functional theory plus dispersion (DFT-D) calculations, we elucidate the mechanism of the reaction and demonstrate that the low activation barrier relies on heterogeneous catalysis at the upper step edges, where low-coordinated surface atoms are present.

High Catalytic Activity and Chemoselectivity of Sub-nanometric Pd Clusters on Porous Nanorods of CeO2 for Hydrogenation of Nitroarenes.

Sub-nanometric Pd clusters on porous nanorods of CeO2 (PN-CeO2) with a high Pd dispersion of 73.6% exhibit the highest catalytic activity and best chemoselectivity for hydrogenation of nitroarenes to date. For hydrogenation of 4-nitrophenol, the catalysts yield a TOF of ∼44059 h(-1) and a chemoselectivity to 4-aminophenol of >99.

Ultrathin rhodium nanosheets.

Despite significant advances in the fabrication and applications of graphene-like materials, it remains a challenge to prepare single-layered metallic materials, which have great potential applications in physics, chemistry and material science. Here we report the fabrication of poly(vinylpyrrolidone)-supported single-layered rhodium nanosheets using a facile solvothermal method. Atomic force microscope shows that the thickness of a rhodium nanosheet is <4 Å.