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Special Report                                                                                                                                                                   Special Report


       production in electrolytic hydrogen pro-  are styrene and ROCO-C-NOH and  Sustainable twist – towards                                                                             and electricity to make ethylene oxide/
       duction; CO  reduction, etc.) Extensive  unconverted styrene can be recovered.   highly atom effi cient Grignard                                                                   ethylene glycol (EG) and propylene oxide/
                2
       research is earmarked on MOR with high  (ACS Sustainable Chem. Eng., 2024,   processes                                                                                            propylene glycol and have carried out a
       Faraday effi ciencies. These authors have  DOI: 10.1021/acssuschemeng.4c03621).                                                                                                    techno-economic analyses. Gas diffusion
       investigated the selectivity of MOR to                             P. Kohler et al have referred to Cu salts                                                                      electrode assembly was used. At single
       formate with progressing conversion at  Combined methane cracking   being highly toxic for aquatic life with                                                                      pass, conversion was above 70% for EO
       high current densities of up to 200 mA per  for H  production with   devastating and long-lasting effects.                                                                        and 40% for EG with overall Faradaic
                                              2
       sq. cm. on the electrodes referred above.   CO  utilised for catalyst   Thus, elimination of Cu should be                                                                         Effi ciencies (FE) above 20% and high
                                            2
       With optimisation, a formate yield of   regeneration using dual    welcome. In Grignard reactions, acyl                                                                           carbon selectivities. Propylene conver-
       70% at 100 mA per sq. cm. with an anodic   functional nanostructured   chlorides are widely used in combina-                                                                      sion realises economic feasibility at a
       potential of 1.33V vs. reversible hydrogen   particles             tion with Cu(I) chloride to introduce      Aldehyde end-capped               cathode to anode. Effi ciency is high;   minimum single-pass conversion of 10%
       electrode (RHE). (Chem. Eng. Jl., 2024,                            acyl substitutes to aromatic compounds.    degradable polyethylenes          even 3.24M formate was produced   and overall, FE greater than 10%. This
       495, 1 Sep., 153000; DOI: 10.1016/j.  Y-C Zeng et al have worked on the title   These authors have demonstrated that   (PEs) from H -controlled   (which can be directly used as anode fuel   route merits consideration. (Green Chem.,
                                                                                                                                   2
       cej.2024.153000).                 problem which allows CO  to be used   carboxylic acids anhydrides are a com-  C H /CO copolymerisation        for fuel cells). (A.I.Ch.E.Jl., 2024; DOI:   2024; DOI: 10.1039/D4GC02672A).
                                                                                                                          4
                                                                                                                       2
                                                                                                                                                       10.1002/aic.18382).
                                                              2
                                         for converting carbon obtained from   petent and highly selective alternative
       Repulsion attractive for          cracking of methane to CO. A Ni-based   to acyl chlorides when used in the   C. Song et al have worked on making   New route for acetylene      Membrane-based electrolytic
       electrocatalysis                                                   absence of Cu(I) catalyst. The carboxy-    degradable  PE plastic via  non-alter-                              production of metals
                                                                                                                     nating copolymerisation of C H  and  synthesis via electrochemical
                                                                          late salt by-products are recycled via                              2  4
       R.V. Mom has reported that unravelling                             reaction with ketene thus eliminating      CO to give PE with in-chain ketones.  formation of metal carbides   The metal oxide-to-metal conversion is
       the key parameters that govern the acti-                           waste and heavy metal outgo. (Helv.        These authors have made such poly-  from CO  in chloride melts      most energy-intensive step. In the US,
                                                                                                                                                                2
       vity of O  evolution reaction catalysts                            Chim. Acta, 2024; DOI: 10.1002/hca.        mers with molecular weight in range                                 these industries emit 100-mtpa of CO .
              2
                                                                                                                                                                                                                       2
       is an essential step towards efficient                             2024000487).                               of 43-195 KDa. Here the hydrogen acts   Y. Suzuki et al have come out with the   Electrolytic process can solve this prob-
       production of green H . The repulsion                                                                         as a chain-transfer agent; end-groups   novel title process utilising the electro-  lem to a considerable extent, but there
                         2
       between adsorbates on the electrocata-                             Micelle-enabled Hofmann                    are aldehydes. This type of polymer is   chemical reduction of CO  in chloride   are problems. In the suggested process
                                                                                                                                                                            2
       lyst surface has been recognised as a   spherical nanoparticle cluster was deve-  rearrangement in water      amenable to photodegradation which   melts. Metal carbides and water give   an oxygen-ion-conducting solid oxide
       powerful promoter for the rate-limiting   loped for effective cyclic catalyst. 10                             produces signifi cantly lower molecular   acetylene. Li C  and CaC  as the metal   membrane SOM) was used as a selective
                                                                                                                                                                   2
                                                                                                                                                                            2
                                                                                                                                                                  2
       O-O coupling step. (Nature Catalysis,   Ni-1Ce/5Al allows high yield of H .   X. Xing et al have converted a variety of   weight polymers and oligomers with   carbides were formed at high current   electrolyte between molten salt and the
       2024, 7, 757-758).                This is achievable at remarkably low   amides to the corresponding amines using   unambiguous vinyl and acetyl terminals.                       anode for making metals and alloys.
                                                                       2
                                                                                                                     (Angew. Chem. Intl. Ed., 2024; DOI:
       Biphasic electrosynthesis of      temperature of around 600°C. (ACS   nanomicelles in water and without use of   10.1002/anie.202410558).                                         Here  metals and/or  their  alloys  are
       2-Isoxazol(in)e-3-carboxylates:   Sustainable Chem. Eng., 2024; DOI:   any solvent. Excellent yield up to 99% are   Electrochemical Processes                                     formed at the cathode and pure O  forms
                                                                                                                                                                                                                   2
                                         10.1021/acssuschemeng.4c04266).
       Reaction optimisation from                                         reported and was scaled-up and proved to   (EPs)                                                               at the anode. Selectivity for O  separa-
                                                                                                                                                                                                                 2
                                                                          be robust. (Org. Proc. Res. Dev., 2024;
       milligram to heterogram scale     Advantageous properties of a     DOI: 10.1021/acs.oprd.4c00197).            [This column has covered many papers                                tion is the key benefi t of the process.
                                                                                                                                                                                         As an example, the authors have cited
       Y. Nakamura et al have reported good   new fungicide, isofetamid (I)                                          on EPs as “Electrons” are “clean” and   effi ciency in two types of melts: LiCl-  solar-grade silicon production where
       yields for the title reaction. The proposed                        Synthesis of peptides                      with the availability of renewable energy   KCl-CaCl -CaO melt at 450°C and   manufacturing cost and energy use are
                                                                                                                                                                2
       strategy has been demonstrated by over   S. Nishimi et al have reported a new   by reactive extrusion:        we can have  distributed production   NaCl-KCl-CaCl -CaO melt at 550°C   reduced by 80-90%. (Chem. Eng. Prog-
                                                                                                                                                                     2
       30 highly functionalised and diverse   fungicide and have assessed its fungal   Application to the continuous   particularly of speciality chemicals.]  and two types of electrodes (Fe, SUS   ress, May 2024).
       examples. Even a derivative isoxadifen-  spectrum, mode of action and effects   and solventless preparation of                                  304, SUS 316, Mo, Ta and Ti) and
       ethyl has been synthesised in a more   on the infection process of  Botrytis   Aspartame (A)                  Concentrated formate              carbon electrodes (graphite) were used.   Catalyst-free PET and
       sustainable way. The starting reactants   Cinerea.  Fungicidal  activity  against                             produced through co-              Acetylene was obtained with a current   PEF polyesters using a
                                         isolates of B. Cinerea resistant existing   T.M. El-Dine et al have carried out pep-  electrolysis of CO  and   effi ciency of 68%. (ACS Sustainable   new traceless oxalate chain
                                                                                                                                       2
                                                    fungicide was studied. I   tide synthesis in a twin-screw extruder.   methanol in a zero-gap       Chem. Eng., 2024, DOI, 10.1021/acs-  extender
                                                    exhibited excellent fungi-  No solvent was used, and excesses of   electrolyser (to make formate)  suschemeng.3c08139).
                                                    cide activity against   starting  material  and  reagents  were                                                                      K. Van der Mass et al have referred to the
                                                    ascomycetes; it had no   avoided. This general method enabled the   J. Lin et al have reported a CO  and   Electrochemical routes for   use of antimony or tin-based catalysts,
                                                                                                                                                2
                                                    activity against basidio-  preparation of dipeptides and tripeptides   CH OH co-electrolysis strategy to   ethylene and propylene    which are used during polymerisation to
                                                                                                                        3
                                                    mycetes and oomycetes.   with no epimerisation. Aspartame, a     produce formate at both electrodes and   oxidation                  make PET and PEF which may create
                                                    (J. Pesticide Sci., 2024,   synthetic dipeptide, was made in a conti-  collect  highly  concentrated  formate                        some problem due to toxicity for food
                                                    49, Issue  2, 130-134;   nuous mode on large scale and with high   in  a  zero-gap  electrolyser. An anion  A.P. Sibal et al have worked on the   packaging. These authors have come out
                                                    DOI; 10.1584/jpesticide   productivity. (Chemistry Europe, 2024, 2,   exchange membrane was employed to  economic feasibility of electrochemical   with a new strategy, which also covers
                                                    D 23-067).            issue 3-4; DOI: 10.1002/ceur.202400007).   enable formate product to move from  oxidations in aq. medium using water   copolyesters with isosorbide, by linking
       168                                                                 Chemical Weekly  November 26, 2024        Chemical Weekly  November 26, 2024                                                              169
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