01902nas a2200193 4500008004100000022001400041245018300055210006900238260000800307300001400315490000700329520113700336100001901473700002901492700002601521700001501547700002001562856012601582 2021 eng d a1463-926200aAn innovative light assisted production of acetic acid from CO2 and methanol: a first photocatalytic approach using a reusable cobalt(ii) molecular hybrid at atmospheric pressure0 ainnovative light assisted production of acetic acid from CO2 and cNOV a9048-90600 v233 aAcetic acid is an important commodity chemical that is produced either by fermentation processes, or more commonly, through chemical routes such as methanol carbonylation with CO and H-2, acetaldehyde oxidation, or hydrocarbon oxidation. More recently, methanol hydrocarboxylation with CO2 and H-2 under thermal catalytic conditions has attracted interest. The synthesis of acetic acid from easily available CO2 is of great significance yet rarely reported. The present paper describes the first photocatalytic approach for the synthesis of acetic acid from methanol and CO2 under ambient reaction conditions without using molecular hydrogen. The maximum conversion of methanol achieved is 60% with a selectivity of 81% towards acetic acid using an octa-sulfur bound cobalt phthalocyanine (CoPc/S8) photocatalyst without an additional sacrificial electron donor. Product analysis, controlled experiments and DFT calculations suggest the formation of methylene carbene as a reactive intermediate. The developed methodology represents a potentially exciting approach for synthesizing acetic acid utilizing CO2 in a sustainable manner.1 aSaini, Sandhya1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aRay, Anjan1 aJain, Suman, L. uhttps://library.ncl.res.in/content/innovative-light-assisted-production-acetic-acid-co2-and-methanol-first-photocatalytic03587nas a2200181 4500008004100000245015100041210006900192260000800261300001600269490000600285520287600291100001603167700001803183700002903201700002603230700002003256856012903276 2024 eng d00aSynergistic combination of ZnCl2/Cu-BTC MOF for the photocatalytic oxidative deamination of benzylamines using CO2 under visible-light irradiation0 aSynergistic combination of ZnCl2CuBTC MOF for the photocatalytic cJUL a2095–21010 v23 a

This paper demonstrates the first CO2-mediated oxidative deamination of benzylamines to benzaldehydes using a combination of ZnCl2 and Cu-BTC MOF as photocatalysts in a carbon tetrachloride solvent under visible-light irradiation. Interestingly, the synergistic combination of ZnCl2 and Cu-BTC afforded the targeted oxidation of benzylamine to benzaldehyde, wherein CO2 acted as an oxidant. The individual components yielded the corresponding imine as the main product, resulting from the oxidative coupling of the benzylamine. DFT calculations and computational studies supported the proposed reaction pathways involving the formation of an intermediate imine from benzylamine via dehydrogenation followed by hydrolysis to produce benzaldehyde. This work, demonstrating the use of CO2 as an oxidant, may open up new avenues for CO2 utilization in chemical production by using sustainable light energy.

1 aKumar, Amod1 aBhatt, Sakshi1 aSamal, Pragnya, Paramita1 aKrishnamurty, Sailaja1 aJain, Suman, L. uhttps://library.ncl.res.in/content/synergistic-combination-zncl2cu-btc-mof-photocatalytic-oxidative-deamination-benzylamines