Photocatalytic Late-Stage C–H Functionalization

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(8), P. 4237 - 4352

Published: Jan. 24, 2023

The emergence of modern photocatalysis, characterized by mildness and selectivity, has significantly spurred innovative late-stage C–H functionalization approaches that make use low energy photons as a controllable source. Compared to traditional strategies, photocatalysis paves the way toward complementary and/or previously unattainable regio- chemoselectivities. Merging compelling benefits with workflow offers potentially unmatched arsenal tackle drug development campaigns beyond. This Review highlights photocatalytic strategies small-molecule drugs, agrochemicals, natural products, classified according targeted bond newly formed one. Emphasis is devoted identifying, describing, comparing main mechanistic scenarios. draws critical comparison between established ionic chemistry photocatalyzed radical-based manifolds. aims establish current state-of-the-art illustrate key unsolved challenges be addressed in future. authors aim introduce general readership functionalization, specialist practitioners evaluation methodologies, potential for improvement, future uncharted directions.

Language: Английский

---

Solar-driven methanogenesis with ultrahigh selectivity by turning down H2 production at biotic-abiotic interface

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: Nov. 3, 2022

Integration of methanogens with semiconductors is an effective approach to sustainable solar-driven methanogenesis. However, the H2 production rate by largely exceeds that methanogen metabolism, resulting in abundant as side product. Here, we report binary metallic active sites (namely, NiCu alloys) are incorporated into interface between CdS and Methanosarcina barkeri. The self-assembled barkeri-NiCu@CdS exhibits nearly 100% CH4 selectivity a quantum yield 12.41 ± 0.16% under light illumination, which not only reported biotic-abiotic hybrid systems but also superior most photocatalytic systems. Further investigation reveal Ni-Cu-Cu hollow alloys can directly supply hydrogen atoms electrons through photocatalysis barkeri for methanogenesis via both extracellular intracellular cycles, effectively turning down production. This work provides important insights interface, offers avenue engineering process.

Language: Английский

---

Photochemistry Journey to Multielectron and Multiproton Chemical Transformation

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(36), P. 16219 - 16231

Published: Sept. 2, 2022

The odyssey of photochemistry is accompanied by the journey to manipulate "electrons" and "protons" in time, space, energy. Over past decades, single-electron (1e-) photochemical transformations have brought marvelous achievements. However, as each photon absorption typically generates only one exciton pair, it exponentially challenging accomplish multielectron proton transformations. multistep differences thermodynamics kinetics urgently require us optimize light harvesting, expedite consecutive electron transfer, interaction catalysts with substrates, coordinate transfer furnish selective bond formations. Tandem catalysis enables orchestrating different events catalytic from subpicoseconds seconds, which facilitates redox chemistries brings consecutive, value-added reactivities. Joint efforts molecular material design, mechanistic understanding, theoretical modeling will bring synthetic opportunities for fuels, fertilizers, chemicals enhanced versatility, efficiency, selectivity, scalability, thus taking better advantage photons (i.e., sunlight) our sustainable society.

Language: Английский

---

Enhanced activity for the oxygen reduction reaction in microporous water

Nature Catalysis, Journal Year: 2023, Volume and Issue: 6(5), P. 425 - 434

Published: May 15, 2023

Language: Английский

---

Bonds over Electrons: Proton Coupled Electron Transfer at Solid–Solution Interfaces

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(13), P. 7050 - 7064

Published: March 21, 2023

This Perspective argues that most redox reactions of materials at an interface with a protic solution involve net proton-coupled electron transfer (PCET) (or other cation-coupled ET). view contrasts the traditional electron-transfer-focused semiconductors, but processes metal surfaces are often described as PCET. Taking thermodynamic perspective, is typically accompanied by stoichiometric proton, much chemistry lithium-ion batteries involves coupled transfers e- and Li+. The PCET viewpoint implicates surface-H bond dissociation free energy (BDFE) preeminent energetic parameter its conceptual equivalents, electrochemical ne-/nH+ potential versus reversible hydrogen electrode (RHE) hydrogenation, ΔG°H. These parameters capture thermochemistry interfaces better than electronic such Fermi energies, chemical potentials, flat-band or band-edge energies. A unified picture semiconductor presented. Exceptions, limitations, implications, future directions motivated this approach described.

Language: Английский

---

Recent Advances of Electrocatalyst and Cell Design for Hydrogen Peroxide Production

Nano-Micro Letters, Journal Year: 2023, Volume and Issue: 15(1)

Published: April 7, 2023

Abstract Electrochemical synthesis of H 2 O via a selective two-electron oxygen reduction reaction has emerged as an attractive alternative to the current energy-consuming anthraquinone process. Herein, progress on electrocatalysts for generation, including noble metal, transition metal-based, and carbon-based materials, is summarized. At first, design strategies employed obtain with high electroactivity selectivity are highlighted. Then, critical roles geometry electrodes type reactor in striking balance boost rate systematically discussed. After that, potential strategy combine complementary properties catalysts optimal overall yield illustrated. Finally, remaining challenges promising opportunities high-efficient electrochemical production highlighted future studies.

Language: Английский

---

Endogenous Photosensitizers in Human Skin

Chemical Reviews, Journal Year: 2023, Volume and Issue: 123(16), P. 9720 - 9785

Published: July 17, 2023

Endogenous photosensitizers play a critical role in both beneficial and harmful light-induced transformations biological systems. Understanding their mode of action is essential for advancing fields such as photomedicine, photoredox catalysis, environmental science, the development sun care products. This review offers comprehensive analysis endogenous human skin, investigating connections between electronic excitation subsequent activation or damage organic biomolecules. We gather physicochemical photochemical properties key examine relationships chemical reactivity, location within primary biochemical events following solar radiation exposure, along with influence on skin physiology pathology. An important take-home message this that photosensitization allows visible light UV-A to have large effects skin. The presented here unveils potential causes continuous increase global cancer cases emphasizes limitations current protection approaches.

Language: Английский

---

A US perspective on closing the carbon cycle to defossilize difficult-to-electrify segments of our economy

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(5), P. 376 - 400

Published: May 1, 2024

Electrification to reduce or eliminate greenhouse gas emissions is essential mitigate climate change. However, a substantial portion of our manufacturing and transportation infrastructure will be difficult electrify and/or continue use carbon as key component, including areas in aviation, heavy-duty marine transportation, the chemical industry. In this Roadmap, we explore how multidisciplinary approaches enable us close cycle create circular economy by defossilizing these difficult-to-electrify those that need carbon. We discuss two for this: developing alternatives improving ability reuse carbon, enabled separations. Furthermore, posit co-design use-driven fundamental science are reach aggressive reduction targets. To achieve net-zero emissions, must industries electrify. Developing needed provide non-fossil accelerate advances towards defossilization.

Language: Английский

---

Ligand-Bound CO₂ as a Nonclassical Route toward Efficient Photocatalytic CO₂ Reduction with a Ni N-Confused Porphyrin

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(15), P. 10550 - 10558

Published: April 8, 2024

Implementing the synergistic effects between metal and ligand has successfully streamlined energetics for CO2 activation gained high catalytic activities, establishing important breakthroughs in photocatalytic reduction. Herein, we describe a Ni(II) N-confused porphyrin complex (NiNCP) featuring an acidic N–H group. It is readily deprotonated exists anion form during catalysis. Owing to this functional site, NiNCP gave rise outstanding turnover number (TON) as 217,000 with 98% selectivity reduction CO, while parent (NiTPP) was found be nearly inactive. Our mechanistic analysis revealed nonclassical reaction pattern where effectively activated via attack of Lewis-basic ligand. The resulting ligand-bound adduct could further reduced produce CO. This new metal–ligand effect anticipated inspire design highly active catalysts small molecule activations.

Language: Английский

---

A molecular-level mechanistic framework for interfacial proton-coupled electron transfer kinetics

Nature Chemistry, Journal Year: 2024, Volume and Issue: 16(3), P. 343 - 352

Published: Jan. 16, 2024

Language: Английский

---