Page 184 - CW E-Magazine (12-11-2024)

Special Report

mediated coupling of CH and CO to reaction when conducted in batch mode namely Ni@TiOx. This catalyst gives
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give AA. The selectivity was as high leads to low reaction rate and low PAP high selectivity for propylene and is
as 92%. (Angew. Chem. Intl. Ed., 2024; yield at low H pressure. Thus these stable under industrially relevant con-
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DOI: 10.1002/anie.202412995). authors went for a continuous-fl ow ditions. This study elucidates the role of
process involving hydrogenation – re- defective TiOx overlayers and the elec-
Restructuring of Ag catalysts arrangement of NB, which provides a tronic promotional effect of catalyst.
for CH OH to HCHO conversion safe, green, and effi cient process. 94.5% (Angew. Chem. Intl. Ed., 2024; DOI:
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studied using in situ X-ray yield of phenyl hydroxylamine (PHA) is 10.1002/anie.202416080).
ptychography and electron reported in THF as a solvent and addi-
microscopy tive 4-dimethylaminopyridine (DMAP). Sulfonic acid-modifi ed MOFs
[The oxidative conversion of CH OH Acid catalysts based Bamberger re- as heterogeneous bifunctional
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to HCHO is practiced on a large scale agent is solvent-sensitive, and PHA was catalysts for ethylene oligomeri-
and Ag based catalysts are used.] mixed with sulphuric acid solution in sation at room temperature
THF solution with a microfl uidic chip. without cocatalysts
S. Das et al have mentioned that under PHA conversion was 100% with a low
reaction conditions polycrystalline Ag H SO concentration at 1wt%. (Org. [Oligomerisation of ethylene to
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experiences surface faceting, formation of Proc. Res. Dev., 2024; DOI: 10.1021/ butene-1, hexene-1, octene-1 and higher
dynamic pinholes like surface pores, and acs.oprd.4c00275). alpha olefi ns is now practiced on
subsequent sintering leading to increased a large scale and plant capacity of
pressure drop and catalyst activity, and Continuous flow intensifi- 450,000-tpa exist.]
cation for the synthesis of Y. Ning et al have reported catalysts
high-purity warfarin (W) which do not require methylalumin-
oxane (MAO), Al alkyl, and other cata-
It is interesting that W was fi rst intro- lysts. Three sulfonic acid-modifi ed
duced as a rodenticide, and is now pre- MOFs [SA/MIL-101 (Cr), UiO-66-
scribed for preventing clotting of blood. NS and MIL-101 (Cr)-NS)] were pre-
D.V. Silva-Brenas et al have reported a pared and used at room temperature.
after several months catalyst has to be highly intensifi ed continuous process These exhibited excellent performance
replaced. The title investigation have leading to 85% isolated yield, using with C-8 alpha olefi n yield at 70.3%.
revealed that bubble formation within benign solvent and purity above 97%, Thus tetramerisation of C H has been
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catalysts of 5 to 8 µm thickness was by simple precipitation in acid. Chemi- shown. (Cat. Sci. Technol., 2024; DOI:
visualised in real-time using in situ X-ray stry is reported in the paper. (Org. Proc. 10.1039/D4CY00502C).
ptychography. This extensive study Res. Dev., 2023; DOI: 10.1021/acs.
provides clues of catalyst functioning oprd.3c00338). Mn carbodiimide (Mn NCN):
and should be helpful in devising more A new heterogeneous Mn cata-
sturdy catalysts. (Catalysis Sci. Technol., A smart design of non-noble lyst for the selective synthesis
2024; DOI: 10.1039/D4CY00770K). catalysts for sustainable of nitriles from alcohols

Study on continuous-fl ow propane (P) dehydrogenation Z. Zhang et al have worked on Mn-
process for direct synthesis of (PDH) based catalysts, as only MnOx catalysts
p-aminophenol (PAP) from [Dehydrogenation of P to propylene is are not satisfactory. Mn NCN was used
now practiced on a grand scale and
nitrobenzene plant capacities upto 750,000-tpa have for ammoxidation of alcohols into
[PAP, the key intermediate for the well- been created, but all of them use noble nitriles and this avoids over-oxidation
known drug, paracetamol, is extensively metal based catalysts.] and the hydrolysis of nitriles. This new
made from p-nitrochlorobenzene via catalyst has high activity and selecti-
hydrolysis and hydrogenation. However, G.J. Hutchings et have referred to the vity and wide applicability to substrate,
the cheapest route is the so-called work of Gong and coworkers who have which include substituted aliphatic al-
one step process from NB. This is domi- reported a breakthrough discovery for cohols, and diols. DFT calculations
nated by one large company globally.] PDH by introducing a sustainable cata- were done. Mechanism is explained.
lyst consisting of titanium oxide over- (Agnew. Chem. Intl. Ed., 2024; DOI:
J. Huang et al have reported the title layers encapsulating Ni nanoparticles, 10.1002/anie.202413799).

184 Chemical Weekly November 12, 2024

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