Catalytic Hydrogenolysis by Atomically Dispersed Iron Sites Embedded in Chemically and Redox Non-innocent N-Doped Carbon.

Atomically dispersed first-row transition metals embedded in nitrogen-doped carbon materials (M-N-C) show promising performance in catalytic hydrogenation but are less well-studied for reactions with more complex mechanisms, such as hydrogenolysis. Their ability to catalyze selective C-O bond cleavage of oxygenated hydrocarbons such as aryl alcohols and ethers is enhanced with the participation of ligands directly bound to the metal ion as well as longer-range contributions from the support. In this article, we describe how Fe-N-C catalysts with well-defined local structures for the Fe sites catalyze C-O bond hydrogenolysis. The reaction is facilitated by the N-C support. According to spectroscopic analyses, the as-synthesized catalysts contain mostly pentacoordinated FeIII sites, with four in-plane nitrogen donor ligands and one axial hydroxyl ligand. In the presence of 20 bar of H2 at 170-230 °C, the hydroxyl ligand is lost when N4FeIIIOH is reduced to N4FeII, assisted by the H2 chemisorbed on the support. When an alcohol binds to the tetracoordinated FeII sites, homolytic cleavage of the O-H bond is accompanied by reoxidation to FeIII and H atom transfer to the support. The role of the N-C support in catalytic hydrogenolysis is analogous to the behavior of chemically and redox-non-innocent ligands in molecular catalysts based on first-row transition metal ions and enhances the ability of M-N-Cs to achieve the types of multistep activations of strong bonds needed to upgrade renewable and recycled feedstocks.

Transfer hydrogenation of phenol over Co-CoOx/N-doped carbon: boosted catalyst performance enabled by synergistic catalysis between Co0 and Coδ.

Selective hydrogenation of biomass-derived phenols into cyclohexanones or cyclohexanols is an industrially important fundamental reaction. Traditional processes commonly used noble metal catalysts and high-pressure H2 as a donor, which are not cost-saving and selectivity-controllable. Herein, we fabricated highly dispersed cobalt nanoparticles (<5 nm) supported on mesoporous N-doped carbon spheres (Co-CoOx/NCS) via an ion exchange-pyrolysis strategy, which showed excellent activity and good selectivity in one-pot transfer hydrogenation of phenol to cyclohexanol with 2-PrOH as a hydrogen donor. It was found that the surface cobalt species of Co-CoOx/NCS could be tuned by simply adjusting the pyrolysis temperature, thus resulting in a boosted catalytic performance of Co-CoOx/NCS-600 (obtained at 600 °C), which was more active than other counterparts as well as Co/NCS-600 and Co3O4/NCS-600. Controlled experiments revealed that Co0 was mainly responsible for dehydrogenation of 2-PrOH, while phenol hydrogenation could be promoted by Lewis acidic Coδ+ (especially by Co2+), and the coexistence of Co0 and Coδ+ was indispensable for boosting the CTH activity of Co-CoOx/NCS. This work provides an economical and environmentally-friendly method for the selective hydrogenation of phenols into value-added chemicals.

General Synthetic Strategy to Ordered Mesoporous Carbon Catalysts with Single-Atom Metal Sites for Electrochemical CO2 Reduction.

The electrochemical carbon dioxide reduction reaction (CO2 RR) is a transformative technology to reduce the carbon footprint of modern society. Single-site catalysts have been demonstrated as promising catalysts for CO2 RR, but general synthetic methods for catalysts with high surface area and tunable single-site metal composition still need to be developed to unambiguously investigate the structure-activity relationship crossing various metal sites. Here, a generalized coordination-condensation strategy is reported to prepare single-atom metal sites on ordered mesoporous carbon (OMC) with high surface areas (average 800 m2  g-1 ). This method is applicable to a broad range of metal sites (Fe, Co, Ni, Cu, Pt, Pd, Ru, and Rh) with loadings up to 4 wt.%. In particular, the CO2 RR to carbon monoxide (CO) Faradaic efficiency (FE) with Ni single-site OMC catalyst reaches 95%. This high FE is maintained even under large current density (>140 mA cm-2 ) and in a long-term study (14 h), which suits the urgently needed large-scale applications. Theoretical calculations suggest that the enhanced activity on single-atom Ni sites results from balanced binding energies between key intermediates, COOH and CO, for CO2 RR, as mediated by the coordination sphere.

Metal-free carbocatalyst for room temperature acceptorless dehydrogenation of N-heterocycles.

Catalytic dehydrogenation enables reversible hydrogen storage in liquid organics as a critical technology to achieve carbon neutrality. However, oxidant or base-free catalytic dehydrogenation at mild temperatures remains a challenge. Here, we demonstrate a metal-free carbocatalyst, nitrogen-assembly carbons (NCs), for acceptorless dehydrogenation of N-heterocycles even at ambient temperature, showing greater activity than transition metal-based catalysts. Mechanistic studies indicate that the observed catalytic activity of NCs is because of the unique closely placed graphitic nitrogens (CGNs), formed by the assembly of precursors during the carbonization process. The CGN site catalyzes the activation of C─H bonds in N-heterocycles to form labile C─H bonds on catalyst surface. The subsequent facile recombination of this surface hydrogen to desorb H2 allows the NCs to work without any H-acceptor. With reverse transfer hydrogenation of various N-heterocycles demonstrated in this work, these NC catalysts, without precious metals, exhibit great potential for completing the cycle of hydrogen storage.

Transition metal-like carbocatalyst.

Catalytic cleavage of strong bonds including hydrogen-hydrogen, carbon-oxygen, and carbon-hydrogen bonds is a highly desired yet challenging fundamental transformation for the production of chemicals and fuels. Transition metal-containing catalysts are employed, although accompanied with poor selectivity in hydrotreatment. Here we report metal-free nitrogen-assembly carbons (NACs) with closely-placed graphitic nitrogen as active sites, achieving dihydrogen dissociation and subsequent transformation of oxygenates. NACs exhibit high selectivity towards alkylarenes for hydrogenolysis of aryl ethers as model bio-oxygenates without over-hydrogeneration of arenes. Activities originate from cooperating graphitic nitrogen dopants induced by the diamine precursors, as demonstrated in mechanistic and computational studies. We further show that the NAC catalyst is versatile for dehydrogenation of ethylbenzene and tetrahydroquinoline as well as for hydrogenation of common unsaturated functionalities, including ketone, alkene, alkyne, and nitro groups. The discovery of nitrogen assembly as active sites can open up broad opportunities for rational design of new metal-free catalysts for challenging chemical reactions.

Facile Fabrication of Hierarchical MOF-Metal Nanoparticle Tandem Catalysts for the Synthesis of Bioactive Molecules.

Multifunctional metal-organic frameworks (MOFs) that possess permanent porosity are promising catalysts in organic transformation. Herein, we report the construction of a hierarchical MOF functionalized with basic aliphatic amine groups and polyvinylpyrrolidone-capped platinum nanoparticles (Pt NPs). The postsynthetic covalent modification of organic ligands increases basic site density in the MOF and simultaneously introduces mesopores to create a hierarchically porous structure. The multifunctional MOF is capable of catalyzing a sequential Knoevenagel condensation-hydrogenation-intramolecular cyclization reaction. The unique selective reduction of the nitro group to intermediate hydroxylamine by Pt NPs supported on MOF followed by intramolecular cyclization with a cyano group affords an excellent yield (up to 92%) to the uncommon quinoline N-oxides over quinolines. The hierarchical MOF and polyvinylpyrrolidone capping agent on Pt NPs synergistically facilitate the enrichment of substrates and thus lead to high activity in the reduction-intramolecular cyclization reaction. The bioactivity assay indicates that the synthesized quinoline N-oxides evidently inhibit the proliferation of lung cancer cells. Our findings demonstrate the feasibility of MOF-catalyzed direct synthesis of bioactive molecules from readily available compounds under mild conditions.

Porous N-Doped Carbon-Encapsulated CoNi Alloy Nanoparticles Derived from MOFs as Efficient Bifunctional Oxygen Electrocatalysts.

A porous N-doped carbon-encapsulated CoNi alloy nanoparticle composite (CoNi@N-C) was prepared using a bimetallic metal-organic framework composite as the precursor. The optimal prepared Co1Ni1@N-C material at 800 °C exhibited well-defined porosities, uniform CoNi alloy nanoparticle dispersion, a high doped-N level, and scattered CoNi-N x active sites, therefore affording excellent oxygen catalytic activities toward the reduction and evolution processes of oxygen. The oxygen reduction (ORR) onset potential ( Eonset) on Co1Ni1@N-C was 0.91 V and the half-wave potential ( E1/2) was 0.82 V, very close to the parameters recorded on the Pt/C (20 wt Pt%) benchmark. Moreover, it is worth noting that the ORR stability of Co1Ni1@N-C was prominently higher than that of Pt/C. Under the oxygen evolution reaction condition, Co1Ni1@N-C generated the maximum current density at the potential of 1.7 V (8.60 mA cm-2) and the earliest Eonset (1.35 V) among all Co xNi y@N-C hybrids. The Co1Ni1@N-C catalyst exhibited the smallest Δ E value, confirming the superior bifunctional activity. The high surface area and porosity, and CoNi-N x active sites on the carbon surface including the proper interactions between the N-doped C shell and CoNi nanoparticles were attributed as the main contributors to the outstanding oxygen electrocatalytic property and good stability.

High-Rota Synthesis of Single-/Double-/Multi-Unit-Cell Ti-HSZ Nanosheets To Catalyze Epoxidation of Large Cycloalkenes Efficiently.

This work first reports high-efficiency epoxidation of large cycloalkenes (carbon number ≥ 7) with tert-butyl hydroperoxide (TBHP) over single-/double-/multi-unit-cell nanosheet-constructed hierarchical zeolite, which is synthesized by one-step hydrothermal crystallization using piperidine as the structure-directing agent of the microporous structure. The excellent catalytic property of the material is ascribed to its unique structural characteristic. Plenty of surface titanols or silanols on the surface of MWW nanosheets are beneficial for the formation of transition-state intermediates; a large number of intercrystalline mesopores in the shell of the material not only facilitate the formation of the intermediate for TBHP but also have nearly no hindrance for the diffusion and mass transfer of bulky cycloalkene to the above intermediates; the 12-MR side cups penetrating into the crystals from the external surface are exposed as much as possible to the reaction system because of the single-/double-/multi-unit-cell MWW nanosheet, serving as the primary reaction space for the epoxidation of bulky cyclic alkene and oxidants and providing enough space for the transition state of Ti-OOtBu and bulky cycloalkane. Moreover, an efficient calcination-free catalytic reaction-regeneration method is developed to overcome the challenge for the recyclability of microporous Ti-zeolite in the catalytic epoxidation of bulky cycloalkenes.

Microwave-activated Ni/carbon catalysts for highly selective hydrogenation of nitrobenzene to cyclohexylamine.

Biocarbon supported Ni catalysts have been prepared by facile impregnation of Ni species by microwave-heating and used for selective hydrogenation of nitrobenzene to cyclohexylamine. These catalysts were characterized by X-ray diffraction, Raman spectra, N2 sorption measurement, X-ray photoelectron spectroscopy, temperature programmed reduction of H2 and H2 temperature-programmed desorption. The morphology and particle size of catalysts were imaged by scanning electron microscope and transmission electron microscope. For the hydrogenation of nitrobenzene to cyclohexylamine, 10%Ni/CSC-II(b) exhibits the best catalytic activity to achieve 100 mol% conversion of nitrobenzene and 96.7% selectivity of cyclohexylamine under reaction conditions of 2.0 MPa H2 and 200 °C, ascribed to high dispersion of Ni species and formation of nanosized Ni particles on the support aided by microwave-heating. Thus-prepared Ni/CSC catalyst is greatly activated, in which the addition of precious metal like Rh is totally avoided.

One-pot rota-crystallized hollownest-structured Ti-zeolite: a calcination-free and recyclable catalytic material.

A hydrothermal rota-crystallization method is developed for the one-step synthesis of a hollownest-structured zeolite precursor with the shell composed of autogenously-intergrown MWW nanosheet crystals containing a large number of stacking-pores without using any porogen or hard scaffold. This material possesses a large external surface area. By simple acid washing, the resultant Ti-containing catalyst can be directly used in the epoxidation of alkenes with hydrogen peroxide. The excellent catalytic activity over the Ti-HSZ catalyst is assumed to be due to the exposure of more Ti active sites over the MWW nanosheet crystals in the shell of the catalyst. More importantly, this Ti-HSZ catalyst washed with H2O2/ethanol solution has been reused 6 times without an appreciable decrease in both the conversion of the allyl chloride and the selectivity of the epichlorohydrin, which is ascribed to the structural stability of the hollownest-structured zeolite.

Production of aviation fuel via catalytic hydrothermal decarboxylation of fatty acids in microalgae oil.

A series of fatty acids in microalgae oil, such as stearic acid, palmitic acid, lauric acid, myristic acid, arachidic acid and behenic acid, were selected as the raw materials to produce aviation fuel via hydrothermal decarboxylation over a multi-wall carbon nanotube supported Pt catalyst (Pt/MWCNTs). It was found that Pt/MWCNTs catalysts exhibited higher activity for the hydrothermal decarboxylation of stearic acid with a 97% selectivity toward heptadecane compared to Pt/C and Ru/C under the same conditions. And Pt/MWCNTs is also capable for the decarboxylation of different fatty acids in microalgae oil. The reaction conditions, such as Pt/MWCNTs loading amount, reaction temperature and time were optimized. The activation energy of stearic acid decarboxylation over Pt/MWCNTs was calculated (114 kJ/mol).