Page 166 - CW E-Magazine (9-4-2024)

Special Report Special Report Special Report

Special Report
making syngas [This subject continues to Selective propylene (P) prevent dehydrochlorination. These more favourable overoxidation to N . A Small Co nanoparticles favour
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attract a lot of attention and some papers synthesis authors have developed a series of molecular Ru catalyst has now fl ipped reverse water-gas shift reac-
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have been covered in this column]. Grand [P via PDH is now commercial on a bimetallic PtM/ -Al O (M=Co, Cu, the script, circumventing the thermo- tion over methanation under

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Special Report
scientifi c efforts have been put in to study large scale.] Ni, Fe, Zn, Ga and Sn) and trimetal- dynamic challenges to selectively gene- CO hydrogenation conditions
the C-H activation, yet substantial limi- lic PtCuCo / -Al O to get enhanced rate H. (Nature Catalysis, 2023, 6, 2
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tations inhibit the translation of these Wang et al have reported an intensifi ed selectivity of PCA and suppress the for- 868-869). X. Zhou et al have referred to Co-based
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concepts into industrial practice. Recent approach where PDH is combined with mation of aniline. PtCo/ -Al O gave catalysts as well known for Fischer-
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developments have been reviewed with chemical looping-selective H com- highest hydrogenation activity. On the Direct synthesis of H by effi - Tropsch (F-T) products. These authors
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respect to thermochemical, photochemical, bustion under anaerobic conditions in other hand, PtCu/ -Al O gave highest cient electrochemical Ru-cata- have brought out the signifi cance of
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electrochemical, and non-thermal plasma. a tandem manner. (Nature Catalysis, selectivity of PCA and 97.3% selecti- lysed NH oxidation Co particle size on the selectivity.
Incorporation of product protection 2023, 6, p743). To overcome the limitations of existing vity was realised. (Applied Catalysis A: 3 While the smallest Co nanoparticles
schemes are receiving attention. (Nature ML, these authors have proposed an General, 2023, 666, 25 Sep., 119424; G. Chen et al have reported that Ru show methanation activity, larger ones
Catalysis, 2023, 6, 748-762). Selective conversion of cyclo innovative AI workfl ow that integrates DOI: 10.1016/j.apcata.2023.119424). complexes bearing 2-[5-(pyridin-2-yl)- remain mostly metallic to support
hexene to 2-methoxycyclo- large-language models (LLMs), Baye- New effi cient catalysts based 1H-pyrrol-2-yl] pyridine ligands dis- reverse water-gas shift reaction.
Research progress in electro- hexanol over molybdenum oxide sian optimisation, and active learning play high catalytic activity for the (Angew. Chem. Intl. Ed.; DOI: 10.1002/
chemical/photochemical utilisa- on siliceous beta zeolite loop to expedite and enhance catalyst on hydrotalcite for synthesis of direct electrochemical oxidation of NH anie.202314274).
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tion of CH OH (M) as a C1 optimisation. This strategy was used sandalwood-type fragrances to H, in acetonitrile. The mechanism is
source 3 L. Liu et al have reported the title reac- to optimise the catalyst synthesis of I. Paterova et al have reported bifunctio- explained. (Nature Catalysis, 2023, 6, Reductive amination of 1,6-hexa-
tion giving the trans product in as high ammonia. The versatility of the proposed nal catalysts based on hydrotalcites (HT) 949-958). nediol with a modified Ru/
Utilising of M as a source for other as 95% yield in the presence of metha- method has been pointed out. (Ind. Eng. for one-pot synthesis of 2-methyl-4- Al O catalyst
high-value chemicals is receiving a lot nol and tert-butyl hydroperoxide as an Chem. Res., 2023; DOI: 10.1021/acs. (2,2,3-trimethylcyclopent-3-en-1-yl)-but- Methane (M) oxidation by cata- 2 3
of attention. This review covers this iecr.3c02520). 2-enol, known as Santalinol (S), which lyst reduction L. Zhang et al have reported the title
has a strong scent of sandalwood. This [Valorisation of M, particularly through green process with a newly modifi ed
Room temperature tandem direct oxidation to CH OH, has attrac- Ru-based catalyst and here the active
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conversion of cyclic alkenes ted attention over several years and this Ru species were highly dispersed and
Special Report
into 1,2-diols column has covered some papers.] anchored by the CN species formed
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subject and methylation, methoxy- L. Wang and F-S. Xiao have reported from 1,10-phenanthroline. The yield
of HMDA could reach 54%. (Applied
lation, hydroxymethylation, and cycli- S. Su et al have used four kinds of a reduced phosphomolybdate catalyst, Catalysis A: General, 2024, 669, 5
sation under the conditions of light and nanosized MnO specimens, including where H is required to keep the cata- Jan, 119509; DOI: 10.1016/j.apca-
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electricity. The mechanisms of these α-, β-, and -MnO , which were hydro- lyst surface in a reduced state, for the ta.2023.119509).

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reactions are discussed. (Green Chem., thermally synthesised and used as hetero- above conversion, and productivity as
2023; DOI: 10.1039/D3GC02106H). oxidant. Thus, epoxidation and solvo- geneous catalysts for the room tem- high as 67.4 µmol per gm catalyst per Pd/Au and Pd/Sn catalysts for
lysis are carried out. Other alkoxy- perature conversion of cyclohexene synthesis involves the aldol condensation hour is reported. (Nature Catalysis,
Propane metathesis and hydro- alcohols can be similarly made. (Ind. Eng. into 1,2-cyclohexanediol using O 2023, 6, 866-867). the direct synthesis of H O 2
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genolysis over Ti hydride cata- Chem. Res., 2023; DOI: 10.1021/acs. and isobutyraldehyde as co-oxidant. of campholenic aldehyde with propanal [The direct conversion of H +O to
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to form Santalinal which on hydroge-
lysts iecr.3c02846). β-MnO proved to be good with 99.2% nation gives S. Pd (II) acetylacetonate Tert-butyl hydroperoxide H O has attracted attention for a long
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time and it is a “dream” process and
[Metathesis of olefi nic compounds has conversion of cyclohexene; 73.6% 1,2 proved to be most advantageous. (Cata- (TBHPO) from tert-butanol this column has covered many papers
been commercialised, apart from fetch- Artifi cial intelligence (AI) diol was realised. The catalyst was lysis Today, 2024, 427, 1 Feb., 114405; and H O on this subject.]
st
ing Nobel Prize.] workfl ow for catalyst design reused 10 times. (Green Chem., 2023; DOI: 10.1016/j.cattod. 2013.114405). 2 2
and optimisation DOI: 10.1039/D3GC02863A). Hydrazine (H) M-T El Kfoury et al have reported the D. Kovacic et al have evaluated the
N.S. Lai et al have opined that for Bimetallic and trimetalic Pt- [H is a very valuable substance, which use of heterogeneous rather than homo- promotive effect of Au and Sn to Pd
geneous H SO as a catalyst, which nanoparticles and these do lead to
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novel catalyst development to address based catalysts for selective has multifarious uses. It is usually leads to waste disposal. Cation ex- enhancement in the catalytic acti-
pressing environmental concerns and hydrogenation of p-chloronitro- made via oxidation of NH with H O .] change resin, Amberlyst 15, was used vity of Pd. Under optimised condi-
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energy demand, conventional design benzene (PNCB) to p-chloro- Defying thermodynamics to when the main product is TBHPO and tions both strategies give comparable
M. Huang et al have worked on meta- and optimisation methods fall short aniline synthesise H some di-tert-butyl peroxide and peroxy- results. It seems the optimal PdSn cata-
thesis of propane over 2-5 metal due to the complexity and various para- ketal are formed as by products. lyst achieves superior H O selectivi-
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hydrides. TiH gave the highest butane meters. Machine Learning (ML) has come A. Xiao et al have worked on the P. Garrido-Barros and I. Funes-Ardois Temperature range was 30-50°C. (Can. ties compared to the Pd/Au analogue.
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yield. (Cat. Sci. Technol., 2023; DOI: out with a new era for catalyst optimi- title process of considerable industrial have discussed electrochemical oxida- J. Chem. Eng., 2023; DOI: 10.1002/ (Green Chem., 2023; DOI: 10.1039/
10.1039/D3CY01187A). sation and get over existing problems. importance where it is important to tion of NH , which is out-competed by cjce.25136). D3GC03706A).
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166 Chemical Weekly April 9, 2024 Chemical Weekly April 9, 2024 167
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