Dalton Transactions

doi: 10.1039/d4dt90202epmid: N/A

doi: 10.1039/d4dt90203cpmid: N/A

doi: 10.1039/d4dt90204apmid: N/A

Zhang, Ying; Wang, Xilun; Wang, Ziyue; Liu, Liyang; He, Xiaohui; Ji, Hongbing

doi: 10.1039/d4dt02460epmid: 39377764

Hydrogen peroxide (H2O2) is a valuable clean chemical, which is widely applied in modern industrial production. In the past few decades, H2O2 has been mainly produced industrially by the anthraquinone method, but the process is complicated and energy consuming, which is only economical for large-scale production and is harmful to the environment. The direct synthesis of H2O2 is considered a promising process to replace the anthraquinone method with high atomic economy, no hazardous by-products, and convenient operation, which has attracted much attention. In this review, we systematically present the recent advances in tuning the microenvironment of Pd-based catalysts for enhancing the performance of the direct synthesis of H2O2, including the modulation of active sites and support, from the viewpoint of the reaction mechanism. Finally, a summary and perspective on the most pressing issues and associated untapped research prospects with the direct synthesis of H2O2 are discussed. The purpose of this review is to provide in-depth insights and guidelines to promote the development of novel catalysts for the direct synthesis of H2O2.

Zhao, Mengyun; Liu, Qingqing; Feng, Yeqin; Lv, Hongjin

doi: 10.1039/d4dt02357apmid: 39385676

The photocatalytic hydrogen evolution reaction has been considered as an efficient route to addressing energy and environmental issues. As an interesting class of multi-electron transfer catalysts, polyoxometalates (POMs) have been widely used for photocatalytic hydrogen evolution due to their tunable geometrical and electronic structures, reversible electron storage capacity, and preeminent redox properties. This Frontier article highlights our recent advances in the construction of efficient POM-based photocatalytic hydrogen evolution systems in terms of three aspects, including polyoxometalate-based catalysts, light-absorbing photosensitizers, and sacrificial reagents.

Jenkins, David T.; Trodden, Elizabeth C.; Andresen, John M.; Mansell, Stephen M.; McIntosh, Ruaraidh D.

doi: 10.1039/d4dt02831gpmid: 39523835

A switchable, solvent-free catalytic system was developed in which Al methyl aminebis(phenolate) catalysts selectively initiate the formation of a polyether from cyclohexene oxide under CO2 atmosphere or the ring opening copolymerisation (ROCoP) of cyclohexene oxide and CO2 through the addition of a PPNCl (bis(triphenylphosphine)iminium chloride) cocatalyst to form poly(cyclohexene carbonate).

Li, Yue; Xu, Mingming; Liu, Hongyan; Wang, Xiaokang; Wang, Yutong; Sun, Meng; Fan, Weidong; Sun, Daofeng

doi: 10.1039/d4dt02592jpmid: 39523989

The rational design of metal–organic framework adsorbents is crucial for target gas separation. Herein, we report two three-dimensional MOFs with different topologies by regulating metal ions with amino-functionalized V-type ligands. Adsorption isotherms and Grand Canonical Monte Carlo simulation reveal that UPC-122 with channel-cavity structure has the potential to separate C2H2/C2H4 at room temperature with a separation ratio of 2.35 (50/50).

Rodríguez, Humberto A.; Cruz, Daniel A.; Lavín, Víctor; Padrón, Juan I.; Lorenzo-Luis, Pablo

doi: 10.1039/d4dt02044hpmid: 39466644

This research embarked on the study of a new binaphthyl phosphate scaffold of copper. There are two independent neutral complexes in the asymmetric unit: Cu1/Cu2 (I) and Cu3/Cu4 (II) from a similar structure to paddle-wheel-like, with one arm formed by an intra-hydrogen bond between the water molecule bonded to the copper and the phosphine oxide (PO) moieties. Moreover, in the first complex two water and one ketone molecule complete the coordination sphere of the two-copper metals, instead, in the second one, one water and two ketone molecules. The experimental value obtained for the effective paramagnetic moment indicates that there is no appreciable interaction between the copper(II) cations and that they behave as paramagnetic ions over the entire temperature range explored (5–350 K).

Lu, Rongdeng; Huang, Tinghui; Goloveshkin, Alexander; Kopytov, Dmitry; Orekhova, Kseniya; Khanbekov, Ivan; Utochnikova, Valentina V.

doi: 10.1039/d4dt02501fpmid: 39513192

In order to substitute well-studied but hard-to-deposit inorganic cathodoluminescent (CL) compounds with coordination compounds and organic ligands, it is primarily important to establish CL correlation with photoluminescence and increase CL intensity. In this paper, homo- and mixed-ligand 1,4-terephthalates and naphthalene-2,6-carboxylates of europium were studied, including a novel complex (Eu2(nda)3(BPhen)2(H2O)4) whose crystal structure was determined. They were found to display luminescence of various intensities under excitation by fast electrons, which is characteristic of Eu3+. CL intensity correlated with PLQY when the saturation regime was not reached and with PLQY/τ in the saturation regime.

Merkel, Katherine; Santos, Alyssa V. B.; Simpson, Scott

doi: 10.1039/d4dt02650kpmid: 39513418

Density functional theory (DFT) calculations of 57 iron bis(dithiolene)-N-heterocyclic carbene adducts were conducted to determine what parameters predict, and possibly influence, the coordination of these aforementioned adducts. The parameters considered herein include three different types of nuclear magnetic resonance (C-NMR, Se-NMR, and P-NMR) isotropic chemical shifts, the Tolman Electronic Parameter (TEP), the Huynh Electronic Parameter (HEP), and the percent buried volume (%Vbur) of the different N-heterocyclic carbenes (NHCs) calculated from DFT. These parameters were selected based upon prior literature connection to σ-donor ability, π-acidity, and steric effects. The computed values of the properties were compared via multivariable linear regression models to see which properties best predict the Addison τ parameter—a measure of whether the complex would assume the square pyramidal or trigonal bipyramidal geometry. It was determined that a combination of TEP and %Vbur are the best predictors of the τ value, for the parameters considered herein. The inclusion of additional parameters yields mild improvement to the statistical models for the prediction of the τ value.