The direct hydrogenation of CO2 to methanol using hydrogen is regarded as a potential technology to reduce greenhouse gas emissions and the dependence on fossil fuels. For this technology to become feasible, highly selective and productive catalysts that can operate under a wide range of reaction conditions near thermodynamic conversion are required. Here we combine a CO-producing In oxide catalyst with a methane-producing Co catalyst to obtain an In/Co catalyst for CO2 reduction to methanol. Density functional (DFT) simulations demonstrate that the charge transfer between the Co support and the In oxide film leads to enrichment of the surface of indium oxide with O vacancies, which serve as active sites for selective conversion of CO2 to methanol. Moreover, our simulations suggest that CO2 reduction on Co-supported In2O3–x films will preferentially yield methanol, rather than CO and methane. As a result, the prepared In@Co catalysts produce methanol from CO2 with high selectivity (>80%) and productivity (0.86 gCH3OH gcatalyst–1 h–1) at conversion levels close to thermodynamic equilibrium, even at temperatures as high as 300 °C and at moderate pressures (50 bar).

The superoxide (O2•-) ion is a highly reactive oxygen species involved in many diseases; hence, its noninvasive detection is desirable to identify the onset of pathological processes. Here, we employed photoacoustic (PA) spectroscopy, which enables imaging at ultrasound resolution with the sensitivity of optical modality, for the first time to detect O2•-, using stimuli-responsive contrast agents. meso-(3,5-Di-tert-butyl 4-hydroxyphenyl) porphyrins and oxoporphyrinogens were used as PA contrast agents, which trap the O2•- and enable its detection. The trapped O2•- increased the PA signal amplitude of chromophores up to 9.6-fold, and induced a red-shift in the PA signal maxima of up to 225 nm. Therefore, these trigger-responsive probes may be highly valuable as smart diagnostic PA probes to investigate pathological events stimulated by O2•- species.

All-inorganic perovskite nanocrystals (NCs) have emerged as a class of low-cost and high-efficiency light-emitting materials. However, the structure and phase transition behavior of these NCs remain poorly understood. Here, we provide unambiguous evidence that all these properties are associated with structural defects in NCs. Using CsPbCl3 NCs as a model system, we find that the cubic subdomains in highly defective NCs gradually convert to the orthorhombic upon cooling room-temperature quasi-cubic NCs, whereas high-quality cousins, with mixed cubic and orthorhombic subdomains at room temperature, exhibit a significant resistance for such a phase transition. Car-Parrinello molecular dynamics simulations unveil the important role of point defects in triggering a stepwise, reversible phase transition of CsPbCl3 NCs. Importantly, we show that the defect-triggered phase transition also exists in other all-inorganic perovskite NCs. Our findings provide new insight into the structure and phase transition of CsPbX3 NCs and highlight the important role of defects in impacting these properties.

The concept of upcycling postconsumer plastics into higher-value products is attractive, but the challenges remain to develop a cost-effective upcycling scheme, discover property-enhancing structures, and, most importantly, install recyclability into upcycled plastics to enable a circular lifecycle. Reported herein is a convenient and effective strategy to upcycle polyester, exemplified by poly(glycolic acid) (PGA), via transesterification (TEster) in bioderived, commercially available γ-butyrolactone (BL) that serves as both the solvent and comonomer, which generates sequence-defined copolymer poly(GA-co-BL). Owing to the isolated glycolic sequence present in the copolymer created uniquely by TEster, it exhibits much-enhanced thermal stability (≥44 °C) over both homopolymers or copolymers without such sequences. This upconverted copolymer is chemically recyclable, enabling a complete recovery of pure glycolic acid and BL feedstocks.

The photocatalytic water splitting technique is a promising alternative to produce hydrogen using a facile and proficient method. In the current Review, recent progress made in photocatalytic hydrogen evolution reaction (HER) using 2D nanomaterials (NMs) and composite heterostructures is described. The strong in-plane chemical bonds along with weak van der Waals interaction make these materials lucrative for surface-related applications. State-of-the-art protocols designed for the synthesis of 2D NMs is discussed in detail. The Review illustrates density functional theory (DFT)-based studies against the new set of 2D NMs, which also highlights the importance of structural defects and doping in the electronic structure. Additionally, the Review describes the influence of electronic, structural, and surface manipulation strategies. These impact the electronic structures, intrinsic conductivity, and finally output toward HER. Moreover, this Review also provides a fresh perspective on the prospects and challenges existing behind the application and fabrication strategies.

We combine state-of-the art synthesis, simulations, and physical experiments to explore the tunable, responsive character of telechelic star polymers as models for soft patchy particles. We focus on the simplest possible system: a star comprising three asymmetric block copolymer arms with solvophilic inner and solvophobic outer blocks. Our dilute solution studies reveal the onset of a second slow mode in the intermediate scattering functions as the temperature decreases below the θ-point of the outer block, as well as the size reduction of single stars upon further decreasing temperature. Clusters comprising multiple stars are formed and their average dimensions, akin to the single star size, counterintuitively decrease upon cooling. A similar phenomenology is observed in simulations upon increasing attraction between the outer blocks and is rationalized as a result of the interplay between interstar associations and steric repulsion between the star cores. Since our simulations are able to describe the experimental findings reliably, we can use them with confidence to make predictions at conditions and flow regimes that are inaccessible experimentally. Specifically, we employ simulations to investigate flow properties of the system at high shear rates, revealing shear thinning behavior caused by the breakup of interstar associations under flow. On the other hand, the zero-shear viscosity obtained experimentally exhibits a rather weak activation energy, which increases upon rising star concentration. These findings demonstrate the unusual properties of telechelic star polymers even in the dilute regime. They also offer a powerful toolbox for designing soft patchy particles and exploring their unprecedented responsive properties further on.

Domain-based local pair natural orbital coupled cluster approach with single, double, and perturbative triple excitations, DLPNO–CCSD(T), has been applied within a framework of a reduced version of the reaction-based Feller–Peterson–Dixon (FPD) scheme to predict gas phase heats of formation and absolute entropies of silver inorganic and organometallic compounds. First, we evaluated all existing experimental data currently limited by thermodynamic functions of 10 silver substances (AgH, AgF, AgBr, AgI, Ag2, Ag2S, Ag2Se, Ag2Te, AgCN, AgPO2). The mean average deviation between computed and experimental heats of formation was found to be 1.9 kcal/mol. Notably, all predicted heats of formation turned out to be within the error bounds of their experimental counterparts. Second, we predicted heats of formation and entropies for additional 90 silver species with no experimental data available, substantially enriching silver thermochemistry. Combination of gas phase heats of formation ΔHf and entropies S° of AgNO2, AgSCN, Ag2SO4, and Ag2SeO4 obtained in this work, with respective solid-state information, resulted in accurate sublimation thermochemistry of these compounds. Complementation of predicted ΔHf with heats of formation of some neutrals and positive ions produced 33 silver bond strengths of high reliability. Obtained thermochemical data are promising for developing the concepts of silver chemistry. In addition, derived heats of formation and bond dissociation enthalpies, due to their high diversity, are found to be relevant for testing and training of computational chemistry methods.

The direct transformation of CO2 into high-value-added hydrocarbons (i.e., olefins and aromatics) has the potential to make a decisive impact in our society. However, despite the efforts of the scientific community, no direct synthetic route exists today to synthesize olefins and aromatics from CO2 with high productivities and low undesired CO selectivity. Herein, we report the combination of a series of catalysts comprising potassium superoxide doped iron oxide and a highly acidic zeolite (ZSM-5 and MOR) that directly convert CO2 to either light olefins (in MOR) or aromatics (in ZSM-5) with high space–time yields (STYC2-C4= = 11.4 mmol·g–1·h–1; STYAROM = 9.2 mmol·g–1·h–1) at CO selectivities as low as 12.8% and a CO2 conversion of 49.8% (reaction conditions: T = 375 °C, P = 30 bar, H2/CO2 = 3, and 5000 mL·g–1·h–1). Comprehensive solid-state nuclear magnetic resonance characterization of the zeolite component reveals that the key for the low CO selectivity is the formation of surface formate species on the zeolite framework. The remarkable difference in selectivity between the two zeolites is further rationalized by first-principles simulations, which show a difference in reactivity for crucial carbenium ion intermediates in MOR and ZSM-5.

Here, we demonstrate an approach to synthesizing and structurally characterizing three atomically precise anion-templated silver thiolate nanoclusters, two of which form one- and two-dimensional structural frameworks composed of bipyridine-linked nanocluster nodes (referred to as nanocluster-based frameworks, NCFs). We describe the critical role of the chloride (Cl−) template in controlling the nanocluster’s nuclearity with atomic precision and the effect of a single Ag atom difference in the nanocluster’s size in controlling the NCF dimensionality, modulating the optical properties, and improving the thermal stability. With atomically precise assembly and size control, nanoclusters could be widely adopted as building blocks for the construction of tunable cluster-based framework materials.

A rapid and efficient method to remove thiocarbonylthio end groups from polymers prepared by reversible addition–fragmentation chain transfer (RAFT) is described. The elimination process is obtained in less than 1 min by treating the solution of RAFT-synthesized polymers with 5 equiv of trialkylborane (TAB) in the presence of oxygen under an ambient temperature. The versatility of this method was checked on the most relevant families of thiocarbonylthio chain transfer agents (CTA), including dithioesters, trithiocarbonates, dithiocarbamates, and xanthates, carried by the corresponding RAFT-synthesized polymers. UV, NMR, and MALDI-TOF MS characterization results all confirm the complete removal of their terminal CTA groups.