Selective Hydrogenation over Supported Metal Catalysts: From Nanoparticles to Single Atoms

Chemical Reviews, Год журнала: 2019, Номер 120(2), С. 683 - 733

Опубликована: Сен. 24, 2019

Selective catalytic hydrogenation has wide applications in both petrochemical and fine chemical industries, however, it remains challenging when two or multiple functional groups coexist the substrate. To tackle this challenge, "active site isolation" strategy been proved effective, various approaches to isolation have developed. In review, we summarized these approaches, including adsorption/grafting of N/S-containing organic molecules on metal surface, partial covering active surface by oxides either via doping through strong metal-support interaction, confinement nanoparticles micro- mesopores supports, formation bimetallic alloys intermetallics core@shell structures with a relatively inert (IB IIB) nonmetal element (B, C, S, etc.), construction single-atom catalysts reducible metals. Both advantages disadvantages each approach toward discussed for three types chemoselective reactions, alkynes/dienes monoenes, α,β-unsaturated aldehydes/ketones unsaturated alcohols, substituted nitroarenes corresponding anilines. The key factors affecting activity/selectivity, particular, geometric electronic structure sites, are aim extract fundamental principles development efficient selective as well other transformations.

Язык: Английский

---

Homogeneous Catalysis for Sustainable Energy: Hydrogen and Methanol Economies, Fuels from Biomass, and Related Topics

Chemical Reviews, Год журнала: 2021, Номер 122(1), С. 385 - 441

Опубликована: Ноя. 2, 2021

As the world pledges to significantly cut carbon emissions, demand for sustainable and clean energy has now become more important than ever. This includes both production storage of carriers, a majority which involve catalytic reactions. article reviews recent developments homogeneous catalysts in emerging applications energy. The most focus been on hydrogen as several efficient have reported recently (de)hydrogenative transformations promising economy. Another direction that extensively covered this review is methanol Homogeneous investigated from CO

Язык: Английский

---

Strategies and mechanisms of metal–ligand cooperativity in first-row transition metal complex catalysts

Chemical Society Reviews, Год журнала: 2020, Номер 49(24), С. 8933 - 8987

Опубликована: Янв. 1, 2020

The use of metal–ligand cooperation (MLC) by transition metal bifunctional catalysts has emerged at the forefront homogeneous catalysis science.

Язык: Английский

---

Homogeneous manganese-catalyzed hydrogenation and dehydrogenation reactions

Chem, Год журнала: 2020, Номер 7(5), С. 1180 - 1223

Опубликована: Дек. 9, 2020

Язык: Английский

---

Iron- and Cobalt-Catalyzed Asymmetric Hydrofunctionalization of Alkenes and Alkynes

Accounts of Chemical Research, Год журнала: 2021, Номер 54(11), С. 2701 - 2716

Опубликована: Май 20, 2021

ConspectusTransition metal catalyzed asymmetric hydrofunctionalization of readily available unsaturated hydrocarbons presents one the most straightforward and atom-economic protocols to access valuable optically active products. For decades, noble transition catalysts have laid cornerstone in this field, on account their superior reactivity selectivity. In recent years, from an economical sustainable standpoint, first-row, earth-abundant metals received considerable attention, due high natural reserves, affordable costs, low toxicity. Meanwhile, reactions also gained much interest been investigated gradually. However, since chiral ligand libraries for transition-metal catalysis are limited date, development highly enantioselective versions remains a significant challenge.This Account summarizes our efforts developing suitable ligands iron cobalt applications (hydroboration hydrosilylation) alkenes alkynes. design, we envisioned that unsymmetric NNN-tridentate (UNT) scaffolds could promote these transformations with metals. Therefore, several types UNT were designed prepared laboratory, utilizing amino acids as sources. very beginning, oxazoline iminopyridine (OIP) proposed through rational combination nitrogen-containing scaffolds. After systematic survey effects, imine moiety rigid OIP was replaced by conformationally more flexible amine unit, leading construction reactive aminoisopropylpyridine (OAP) ligands. Subsequently, imidazoline (IIP) thiazoline (TIP) altering oxygen atom nitrogen sulfur linkers, respectively. To further expand library, other tridentate containing twisted pincer, anionic, nonrigid backbone synthesized, including iminophenyl oxazolinyl phenylamine (IPOPA) phenyl picolinamide (ImPPA). The efficacy induction has demonstrated sequential alkynes, which exhibit excellent well chemo-, regio-, stereoselectivity broad functional group tolerance. Notably, regio- challenging substrates, such 1,1-disubstituted aryl terminal aliphatic alkenes, achieved. Furthermore, isomerization/hydroboration internal alkynes demonstrates synthetic power catalytic systems. enantioenriched products obtained methodologies be potentially utilized organic synthesis, medicinal chemistry, materials science. We believe continuous field would beneficial catalysis.

Язык: Английский

---

Is the H2 economy realizable in the foreseeable future? Part II: H2 storage, transportation, and distribution

International Journal of Hydrogen Energy, Год журнала: 2020, Номер 45(41), С. 20693 - 20708

Опубликована: Июнь 21, 2020

Язык: Английский

---

Fatty Acids and their Derivatives as Renewable Platform Molecules for the Chemical Industry

Angewandte Chemie International Edition, Год журнала: 2021, Номер 60(37), С. 20144 - 20165

Опубликована: Фев. 22, 2021

Oils and fats of vegetable animal origin remain an important renewable feedstock for the chemical industry. Their industrial use has increased during last 10 years from 31 to 51 million tonnes annually. Remarkable achievements made in field oleochemistry this timeframe are summarized herein, including reduction fatty esters ethers, selective oxidation oxidative cleavage C-C double bonds, synthesis alkyl-branched compounds, isomerizing hydroformylation alkoxycarbonylation, olefin metathesis. The oleochemicals a great variety polymeric materials tremendously, too. In addition lipases phospholipases, other enzymes have found their way into biocatalytic oleochemistry. Important also generated new oil qualities existing crop plants or by using microorganisms optimized metabolic engineering.

Язык: Английский

---

Insights into the Interfacial Effects in Heterogeneous Metal Nanocatalysts toward Selective Hydrogenation

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(12), С. 4483 - 4499

Опубликована: Март 16, 2021

Heterogeneous metal catalysts are distinguished by their structure inhomogeneity and complexity. The chameleonic nature of heterogeneous have prevented us from deeply understanding catalytic mechanisms at the molecular level thus developing industrial with perfect selectivity toward desired products. This Perspective aims to summarize recent research advances in deciphering complicated interfacial effects hydrogenation nanocatalysts design practical clear mechanism nearly selectivity. insights on how three key components (i.e., metal, support, ligand modifier) a nanocatalyst induce effective interfaces determining activity provided. influence not only H2 activation pathway but also interaction substrates be hydrogenated surface hydrogen transfer process. As for alloy nanocatalysts, together electronic geometric ensemble effects, spillover occurring catalytically "inert" utilizing atom active is highlighted. metal–support interface then discussed emphasis involvement ligands located as well cationic species support hydrogenation. organic modifiers, ability both 3D steric manipulate pathways demonstrated. A brief summary finally provided perspective development enzyme-like catalysts.

Язык: Английский

---

Reversible hydrogenation of carbon dioxide to formic acid using a Mn-pincer complex in the presence of lysine

Nature Energy, Год журнала: 2022, Номер 7(5), С. 438 - 447

Опубликована: Май 19, 2022

Abstract Efficient hydrogen storage and release are essential for effective use of as an energy carrier. In principle, formic acid could be used a convenient medium via reversible CO 2 hydrogenation. However, noble metal-based catalysts currently needed to facilitate the (de)hydrogenation, produced during is generally released, resulting in undesirable emissions. Here we report α -amino acid-promoted system hydrogenation using Mn-pincer complex homogeneous catalyst. We observe good stability reusability catalyst lysine amino at high productivities (CO hydrogenation: total turnover number 2,000,000; dehydrogenation: 600,000). Employing potassium lysinate, achieve >80% H evolution efficiency >99.9% retention ten charge–discharge cycles, avoiding re-loading steps between each cycle. This process was scaled up by factor 18 without obvious drop productivity.

Язык: Английский

---

Nitrogen Fixation via Splitting into Nitrido Complexes

Chemical Reviews, Год журнала: 2021, Номер 121(11), С. 6522 - 6587

Опубликована: Май 11, 2021

The large carbon footprint of the Haber–Bosch process, which provides ammonia for fertilizers but also feedstock all nitrogenous commercial products, has fueled quest alternative synthetic strategies to nitrogen fixation. Owing extraordinarily strong N≡N triple bond, key step reaction, i.e., dissociative adsorption N2, requires high temperatures. Since first report in 1995, a wide variety molecular transition metal and f-block compounds have been reported that can fully cleave N2 at ambient conditions form well-defined nitrido complexes. We here provide comprehensive survey current state splitting reactions solution follow-up transfer reactivity. Particular emphasis is put on electronic structure requirements formation suitable precursors their N–N scission prospects synthesis containing products will be discussed, ranging from heterocumulenes organic amines, amides or nitriles via proton coupled electron transfer, carbonylation, electrophilic functionalization derived Accomplishments challenges fixation are presented offer guidelines development catalytic platforms.

Язык: Английский

---