Chem4Energy: a consortium of the Royal Society Africa Capacity-Building Initiative.

The Africa Capacity-Building Initiative is a Royal Society programme funded by the former UK Department for International Development to develop collaborative research between scientists in sub-Saharan Africa and the UK. Initially, four institutions were involved in the Chem4Energy consortium: Cardiff University in the UK and three African partners, the Kwame Nkrumah University of Science and Technology, Ghana, the University of Namibia and the University of Botswana, soon also including the Botswana International University of Science and Technology. The Chem4Energy research programme focused on 'New materials for a sustainable energy future: linking computation with experiment', aiming to deploy the synergy between state-of-the-art computational and experimental techniques to design and optimize new catalysts and semiconductor materials for renewable energy applications, based on materials that are abundant and readily available in African countries. The Chem4Energy consortium has achieved ambitious research goals, graduated seven PhD students and delivered a high-quality cross-disciplinary training programme in materials science and simulation techniques relevant to renewable energy applications. Since 2021, the extended consortium, including North-West University and the Centre for High-Performance Computing in South Africa, has remained active through an annual Chem4Energy conference series, with the sixth meeting taking place in Namibia in April 2025.

A facile synthesis of a novel 4-hydroxyl-3-azo coumarin based colorimetric probes for detecting Hg2+ and a fluorescence turn-off response of 3CBD to Fe3+ in aqueous environment.

Two azo dyes, (E)-3-(benzo[d]thiazol-2-yldiazenyl)-4-hydroxy-2H-chromen-2-one (3CBD) and (E)-4-hydroxy-3-(quinolin-2-yldiazenyl)-2H-chromen-2-one (3CQD), were designed and synthesized using facile methods. The structures were validated through FTIR and NMR spectroscopy. The photophysical property analyses were further studied using UV-Vis and fluorescence spectrophotometers. Consequently, the absorption and emission spectra of 3CBD confirmed its selectivity of Hg2+ and turn-off response to Fe3+. On the other hand, the absorption spectra analysis of 3CQD demonstrated selectivity in the presence of Hg2+. The colorimetric investigations demonstrated a significant visual response specifically for Hg2+, enabling real-time analysis in the corresponding solutions. The presence of other coexisting metal ions does not interfere with the detection of the target metal ion. The fluorescence studies of the two probes revealed that 3CBD was highly fluorescent, which was significantly quenched by Fe3+, upon excitation at 340 nm. Utilizing Job plot analyses, it was determined that the complexes 3CBD-Hg2+ and 3CQD-Hg2+ exhibit a binding stoichiometry of 1 : 1. The association constants for these complexes were measured to be 7.48 × 105 and 9.12 × 105 M-1, respectively, indicating a strong association between both probes and their respective metal ions. Both chemosensors exhibited comparable limits of detection (LOD) and limits of quantification (LOQ) of 0.03 µM and 0.10 µM, respectively. Reversible studies confirmed that only chemosensor 3CQD could serve as a secondary sensor for EDTA. The theoretical studies calculated using Density Functional Theory (DFT) program at B3LYP/6-31G** (Spartan '10 package) level.

An ESIPT-ICT steered naphthylthioic-based ionic probe with dual emissive channels exhibiting CHEF and CHEQ effects.

A naphthylthioic-based emissive probe (M) bearing a hydroxyl and amine group was designed and synthesized via a one-step Schiff base reaction process. The probe was characterized spectroscopically using 1H NMR, UV-Vis and fluorescence spectrophotometers. The probe turned out to be spectroscopically and colorimetrically selective and sensitive to multiple cations and anions. Interestingly, the probe displayed characteristics of excited-state intramolecular proton transfer (ESIPT)-driven dual emissive channels; experiencing fluorescence enhancement upon the molar additions of Al3+ as well as the anions used, events presumably ascribed to chelation fluorescence enhancement (CHEF), hydrogen bonding and deprotonation effects. Moreover, the fluorometric titration with Hg2+ resulted in ratiometric spectral behaviors of M, with the disappearance of the peak at 450 nm, concomitant with the appearance of a new peak at 520 nm, distinguished by a clear isosbestic point, the same behaviors exhibited by Sn2+ and Ag+ analytes towards M. The introduction of all other cations used, resulted in fluorescence quenching, attributable to chelation enhanced fluorescence quenching (CHEQ), thereby inhibiting the ESIPT process. The experiments were all carried out in the aqueous environment medium of DMSO-H2O (9 : 1) at ambient temperature. Theoretical density functional theory calculations were carried out to gain insight into the interaction of M with cations and anions, and their influence on the HOMO-LUMO energy gaps.

Photocatalytic Degradation of Rhodamine B Dye and Hydrogen Evolution by Hydrothermally Synthesized NaBH4-Spiked ZnS Nanostructures.

Metal sulphides, including zinc sulphide (ZnS), are semiconductor photocatalysts that have been investigated for the photocatalytic degradation of organic pollutants as well as their activity during the hydrogen evolution reaction and water splitting. However, devising ZnS photocatalysts with a high overall quantum efficiency has been a challenge due to the rapid recombination rates of charge carriers. Various strategies, including the control of size and morphology of ZnS nanoparticles, have been proposed to overcome these drawbacks. In this work, ZnS samples with different morphologies were prepared from zinc and sulphur powders via a facile hydrothermal method by varying the amount of sodium borohydride used as a reducing agent. The structural properties of the ZnS nanoparticles were analysed by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques. All-electron hybrid density functional theory calculations were employed to elucidate the effect of sulphur and zinc vacancies occurring in the bulk as well as (220) surface on the overall electronic properties and absorption of ZnS. Considerable differences in the defect level positions were observed between the bulk and surface of ZnS while the adsorption of NaBH4 was found to be highly favourable but without any significant effect on the band gap of ZnS. The photocatalytic activity of ZnS was evaluated for the degradation of rhodamine B dye under UV irradiation and hydrogen generation from water. The ZnS nanoparticles photo-catalytically degraded Rhodamine B dye effectively, with the sample containing 0.01 mol NaBH4 being the most efficient. The samples also showed activity for hydrogen evolution, but with less H2 produced compared to when untreated samples of ZnS were used. These findings suggest that ZnS nanoparticles are effective photocatalysts for the degradation of rhodamine B dyes as well as the hydrogen evolution, but rapid recombination of charge carriers remains a factor that needs future optimization.

Insights from density functional theory calculations into the effects of the adsorption and dissociation of water on the surface properties of zinc diphosphide (ZnP2) nanocrystals.

Zinc phosphides (ZnP2 and Zn3P2) are emerging absorber materials for photovoltaic applications owing to their abundancy and non-toxic nature. Herein, we provide a comprehensive characterisation of the surface structure, composition, stabilities, morphology, and electronic properties of both bare and hydrated/hydroxylated low-Miller index surfaces of ß-ZnP2 by means of density functional theory (DFT) calculations. Mechanistic insights into the fundamental aspects of water adsorption and dissociation, including the adsorption geometries, energetics, and structural parameters along the reaction path are systematically characterised. The stabilities of the surfaces under dry and wet conditions are discussed in detail and the predicted phase diagrams for the water adsorption are presented. Using calculated surface energies, we have derived the equilibrium morphology of the ß-ZnP2 nanocrystals under vacuum and upon hydration or hydroxylation. Atomic-level insights into the origin of the incipient oxidation of ß-ZnP2 surfaces are provided through analysis of Bader charges, which reveal that the Zn sites to which H2O and OH species are bound undergo oxidation due to the transfer of charge to the adsorbed species. Adsorption-induced changes to the electronic properties before and after hydration/hydroxylation were characterised by the work function and partial density of states. The results highlight the need for protection of ß-ZnP2 nanocrystals against possible oxidation in the presence of water through post-synthesis organic functionalisation.

A chromo-fluorogenic HMT sensor for Ag+ and the resultant HMT-Ag complex turn-off probe for F- in DMSO: experimental and theoretical studies.

The photophysical properties of Hexamethylenetetramine (HMT) were investigated through physical methods and spectroscopically in dimethyl sulfoxide (DMSO) at ambient temperature. Evidently, HMT turned out as a sensor, selective and sensitive to silver ion (Ag+) only, among other cations, through colorimetric and fluorometric activities (observable by naked eye) and spectrally, both by UV-Vis and fluorescence spectroscopy. The resulting complex pedant (HMT-Ag) is highly responsive to the presence of fluoride ion (F-) in aqueous soluble DMSO, evidenced by changes in absorption spectra as well as fluorescence quenching, upon addition of the respective ions. Consequently, spectral changes induced by the addition of these ions, were consistently concomitant with colour changes, from colourless to light brown (HMT-Ag) to dark brown (HMT-Ag-F) in daylight condition, while bright light blue colour (HMT) to dark blue brownish (HMT-Ag) under UV-light conditions. The experimental results were complimented by theoretical studies, which are well within agreement of one another.

The C2-Symmetry Colorimetric Dye Based on a Thiosemicarbazone Derivative and its Cadmium Complex for Detecting Heavy Metal Cations (Ni2+, Co2+, Cd2+, and Cu2+) Collectively, in DMF.

The field of chemosensing has been experiencing an exponential expansion in recent times, due to increased demands for simpler and user-friendly analytical techniques, in order to combat and confront the challenges of industrial pollutions in the twenty-first century. Metal complex-based chemosensors have received little attention while exhibiting excellent sensing properties, comparing to their organic counterparts. Thus, a thiosemicarbazone-based (H) and its cadmium complex (P) were synthesized, characterized and their photophysical and chemosensing properties were investigated in DMF solvent. The addition of molar equivalents of selected cations (of nitrates or chloride salts) to H and P, produced visually detectable colour changes as well as remarkable spectral shifts. Explicitly, the two probes (H and P) were able to collectively discriminate heavy metal cations such as Cd2+, Co2+, Zn2+, Cu2+, Ni2+, and Ag+, both in DMF, among all other heavy metal cations tested. None of the anions could be detected by H or P, even when the tetrabutylammonium salts (TBAs) were used, the action presumably ascribed to the solvent effect. Thus, H and P can be used to selectively and sensitively detect the presence of heavy metal cations, via naked-eye detectable colour changes in an aqueous soluble solvent such as DMF.

A multi-colorimetric probe to discriminate between heavy metal cations and anions in DMSO-H2O with high selectivity for Cu2+ and CN-: study of logic functions and its application in real samples.

A ditopic multi-colorimetric probe based on the phenylpridyl-thioic moiety (EN) was synthesized via a Schiff base reaction mechanism and characterized using 1H NMR and UV-vis spectroscopy. The colorimetric analyses carried out revealed that EN was capable of discriminating between a number of heavy metal cations via coordination induced charge transfer, as well as between anions through hydrogen bonding induced charge transfer, in DMSO-H2O (9 : 1). In particular, the ditopic probe could spectrally and colorimetrically recognize the most toxic heavy metal cations of Cd2+, Pb2+ and Hg2+, among others, in DMSO-H2O. Additionally, EN was selective and sensitive to the presence of CN-, F-, AcO- and H2PO4 - in the same solvent system as cations. The reversibility and reproducibility studies showed that EN exhibited complementary IMP/INH logic functions, based on colour and spectral switching (ON/OFF), modulated by F-/Al3+. The real time application of the probe was tested on food grade products to detect the presence of F- in toothpastes and mouthwash dissolved in water, as well as cations in underground water (normally saline), which displayed substantial responses. Thus, EN displayed an excellent scope of response and can thus be developed for real time sensing kits, which could be used instantly in on-field analysis. Theoretical studies were conducted to complement the experimental work.

A chromo-fluorogenic probe for detecting water traces in aprotic solvents based on C2-symmetry dianthrimide-hydroxide complexes: experimental and theoretical studies.

A C2-symmetry dianthrimide based probe (D) and its hydroxide complex (D-OH) are reported as a chromo-fluorogenic sensor for rapid and sensitive detection of trace amounts of water in polar aprotic solvents. Based on intramolecular charge transfer in the excited state, the pink-coloured probe binds with the hydroxide ions to induce a colorimetric response of the resulting complex (D-OH), green in colour. The hydroxide based complex is used as a H2O or moisture sensor, tested in DMF and DCM, due to its high instability in moisture-containing organic solvents and paper materials/fabrics. The probe exhibits higher sensitivity towards pure H2O in DMSO with the LOD measured at 0.0067% v/v, perhaps even lower, in DMF (LOD = 0.100% v/v) and DCM (LOD = 0.013% v/v). The dissociation of OH- from D in the presence of H2O is responsible for the colorimetric and fluorometric responses. The litmus test paper strips prepared by adsorbing or coating them with the D-OH complex in DMSO could not be entirely achieved in an open system, due to the highly unstable state of the complex in the presence of water traces or the atmospheric moisture accumulated in the paper materials. The complex D-OH is also highly suspected to compete for adsorbed water in silica gel crystals in desiccators, due to its high affinity towards water molecules. The experimental studies were complemented by theoretical calculations using the Spartan'14 software package, and the computed data are in good agreement with the spectral data.

Correction: A colorimetric probe for the real-time naked eye detection of cyanide and hydroxide ions in tap water: experimental and theoretical studies.

Correction for 'A colorimetric probe for the real-time naked eye detection of cyanide and hydroxide ions in tap water: experimental and theoretical studies' by Veikko Uahengo et al., Analyst, 2019, 144, 6422-6431.

A colorimetric probe for the real-time naked eye detection of cyanide and hydroxide ions in tap water: experimental and theoretical studies.

Herein, a colorimetric sensor (L) based on a naphthyl derivative bearing hydrazone receptors was synthesized via a one-step reaction process, and its recognition properties towards biologically important anions in an acetonitrile-water mixture were investigated by naked-eye observation and UV-Vis and 1H NMR spectroscopy. The molar addition of anions, such as TBAF-, TBAOH-, TBACN- and TBAAcO-, induced a significant red shift in the charge transfer band (Δλ = 73 nm, from 337 nm to 410 nm), in agreement with visible "naked eye" detectable colorimetric activities; in addition, soaked-in-L paper strips were prepared, which could significantly discriminate cyanide (KCN) and hydroxide (NaOH) ions dissolved in tap water via the litmus test method. This study was complemented by density functional theory computations to gain more insight into the interaction between L and anions.

First-principles DFT insights into the structural, elastic, and optoelectronic properties of α and ß-ZnP2: implications for photovoltaic applications.

Binary II-V semiconductors are highly optically active materials, possess high intrinsic mechanical and chemical durability, and have electronic properties ideal for optoelectronic applications. Among them, zinc diphosphide (ZnP2) is a promising earth-abundant absorber material for solar energy conversion. We have investigated the structural, mechanical, and optoelectronic properties of both the tetragonal (α) and monoclinic (ß) phases of ZnP2 using standard, Hubbard-corrected and screened hybrid density functional theory methods. Through the analysis of bond character, band gap nature, and absorption spectra, we show that there exist two polymorphs of the ß phase (denoted as ß 1 and ß 2) with distinct differences in the photovoltaic potential. While ß 1 exhibits the characteristics of metallic compounds, ß 2 is a semiconductor with predicted thin-film photovoltaic absorbing efficiency of almost 10%. The α phase is anticipated to be an indirect gap material with a calculated efficiency limited to only 1%. We have also analysed and gained insights into the electron localization function, projected density of states and projected crystal orbital Hamilton populations for the analogue bonds between the α and ß-ZnP2. In light of these calculations, a number of previous discrepancies have been solved and a solid ground for future employment of zinc diphosphides in photovoltaics has been established.

A naphthoquinone based colorimetric probe for real-time naked eye detection of biologically important anions including cyanide ions in tap water: experimental and theoretical studies.

A naphthoquinone based colorimetric sensor (N) bearing hydrazone receptors in aqueous media was developed and its recognition properties towards biologically important anions in DMSO-water mixture (9 : 1) were investigated using spectroscopic methods. The hydrazone based receptors showed selectivity towards anions (F-, OH-, CN- and AcO-), through naked eye observable colour changes, from green to light blue (F-, CN- and AcO-) and violet (OH-). The colour changes were concomitant with spectral changes. The sensor could also detect the presence of fluoride ions in commercially available toothpastes, through remarkable colour and spectral changes. In addition, test paper strips prepared from N were able to detect the presence of cyanide (KCN) and hydroxide (NaOH) in tap water. The study was complimented by density functional theory computations to have more insight in the interaction between N and the anions.

A Fluoro-Chromogenic Sensor Based on Organic Molecular Framework for Cu2+ and F- in Aqueous Soluble DMSO.

The 2,2'-dinaphtholazobenzene molecular framework (P) was designed, synthesized and characterized. Its absorption and fluorescence properties revealed that P is a dual sensor for copper ions (Cu2+) and fluoride ions (F-) in DMSO. The colorimetric activities were clearly visible by naked eye upon the addition of the two ions. Fluorescence quenching and enhancement were observed when Cu2+ and F- ions were added respectively. Density Functional Theory (DFT) calculations were carried out to provide an insight into the interaction of guest ions (Cu2+ and F-) with P, and to explain how the molecular orbitals were affected. Graphical Abstract ᅟ.