Institute of Chemical and Engineering Sciences

The hybrid organic–inorganic perovskite (CH3NH3)PbI3 may find application in next generation solid-state sensitised solar cells. Although this material and related perovskites were discovered many decades ago, questions remain concerning their diverse structural chemistry and unusual properties. The article presents a review of previous work and provides a detailed description of the preparation, structural characterisation and physical characteristics of (CH3NH3)PbI3. The phase changes exhibited by (CH3NH3)PbI3 have been probed using variable temperature powder and single crystal X-ray diffraction, combined with differential scanning calorimetry, thermogravimetric analysis and phase contrast transmission electron microscopy. The optical band gap for (CH3NH3)PbI3 determined by UV-Visible spectroscopy was compared to values obtained from density-of-state simulation of the electronic band structure.

We present two different ways to fabricate nitrogen-doped graphene (N-graphene) and demonstrate its use as a metal-free catalyst to study the catalytic active center for the oxygen reduction reaction (ORR). N-graphene was produced by annealing of graphene oxide (G-O) under ammonia or by annealing of a N-containing polymer/reduced graphene oxide (RG-O) composite (polyaniline/RG-O or polypyrrole/RG-O). The effects of the N precursors and annealing temperature on the performance of the catalyst were investigated. The bonding state of the N atom was found to have a significant effect on the selectivity and catalytic activity for ORR. Annealing of G-O with ammonia preferentially formed graphitic N and pyridinic N centers, while annealing of polyaniline/RG-O and polypyrrole/RG-O tended to generate pyridinic and pyrrolic N moieties, respectively. Most importantly, the electrocatalytic activity of the catalyst was found to be dependent on the graphitic N content which determined the limiting current density, while the pyridinic N content improved the onset potential for ORR. However, the total N content in the graphene-based non-precious metal catalyst does not play an important role in the ORR process.

Tremendous efforts have been dedicated into the development of high-performance energy storage devices with nanoscale design and hybrid approaches. The boundary between the electrochemical capacitors and batteries becomes less distinctive. The same material may display capacitive or battery-like behavior depending on the electrode design and the charge storage guest ions. Therefore, the underlying mechanisms and the electrochemical processes occurring upon charge storage may be confusing for researchers who are new to the field as well as some of the chemists and material scientists already in the field. This review provides fundamentals of the similarities and differences between electrochemical capacitors and batteries from kinetic and material point of view. Basic techniques and analysis methods to distinguish the capacitive and battery-like behavior are discussed. Furthermore, guidelines for material selection, the state-of-the-art materials, and the electrode design rules to advanced electrode are proposed.

In the last few years there has been a rapid growth in governmental funding and research activities worldwide for CO2 capture, storage and utilization (CSU), due to increasing awareness of the link between CO2 accumulation in the atmosphere and global warming. Among the various technologies and processes that have been developed and are emerging for CSU of CO2, solid CO2-adsorbents are widely applied. In this review, these solid CO2-adsorbents are classified into three types according to their sorption/desorption temperatures: low-, intermediate- and high-temperature adsorbents with temperatures ranging from below 200 °C, between 200–400 °C and above 400 °C, respectively. For each type of solid CO2-adsorbent, the synthesis, interaction mechanism with CO2 and sorption performance, potential applications and problems are reviewed. In the last section, several representative CO2-sorption-enhanced catalytic reactions are discussed. It is expected that this review will not only summarize the main research activities in this area, but also find possible links between fundamental studies and industrial applications.

The Fenton-like process presents one of the most promising strategies to generate reactive oxygen-containing radicals to deal with the ever-growing environmental pollution. However, developing improved catalysts with adequate activity and stability is still a long-term goal for practical application. Herein, we demonstrate single cobalt atoms anchored on porous N-doped graphene with dual reaction sites as highly reactive and stable Fenton-like catalysts for efficient catalytic oxidation of recalcitrant organics via activation of peroxymonosulfate (PMS). Our experiments and density functional theory (DFT) calculations show that the CoN4 site with a single Co atom serves as the active site with optimal binding energy for PMS activation, while the adjacent pyrrolic N site adsorbs organic molecules. The dual reaction sites greatly reduce the migration distance of the active singlet oxygen produced from PMS activation and thus improve the Fenton-like catalytic performance.

Carbon dioxide (CO₂) capture using solid sorbents has been recognized as a very promising technology that has attracted intense attention from both academic and industrial fields in the last decade.

The December 2011 release of a draft United States Food and Drug Administration (FDA) guidance concerning regulatory classification of pharmaceutical cocrystals of active pharmaceutical ingredients (APIs) addressed two matters of topical interest to the crystal engineering and pharmaceutical science communities: (1) a proposed definition of cocrystals; (2) a proposed classification of pharmaceutical cocrystals as dissociable ``API-excipient'' molecular complexes. The Indo U.S. Bilateral Meeting sponsored by the Indo-U.S. Science and Technology Forum titled The Evolving Role of Solid State Chemistry in Pharmaceutical Science was held in Manesar near Delhi, India, from February 2-4, 2012. A session of the meeting was devoted to discussion of the FDA guidance draft. The debate generated strong consensus on the need to define cocrystals more broadly and to classify them like salts. It was also concluded that the diversity of API crystal forms makes it difficult to classify solid forms into three categories that are mutually exclusive. This perspective summarizes the discussion in the Indo-U.S. Bilateral Meeting and includes contributions from researchers who were not participants in the meeting.

Different C–N bonding configurations in nitrogen (N) doped carbon materials have different electronic structures. Carbon materials doped with only one kind of C–N bonding configuration are an excellent platform for studying doping effects on the electronic structure and physical/chemical properties. Here we report synthesis of single layer graphene doped with pure pyridinic N by thermal chemical vapour deposition of hydrogen and ethylene on Cu foils in the presence of ammonia. By adjusting the flow rate of ammonia, the atomic ratio of N and C can be modulated from 0 to 16%. The domain like distribution of N incorporated in graphene was revealed by the imaging of Raman spectroscopy and time-of-flight secondary ion mass spectrometry. The ultraviolet photoemission spectroscopy investigation demonstrated that the pyridinic N efficiently changed the valence band structure of graphene, including the raising of density of π states near the Fermi level and the reduction of work function. Such pyridinic N doping in carbon materials was generally considered to be responsible for their oxygen reduction reaction (ORR) activity. The 2e reduction mechanism of ORR on our CNxgraphene revealed by rotating disk electrode voltammetry indicated that the pyridinic N may not be an effective promoter for ORR activity of carbon materials as previously expected.

Scanning electron microscopy, X-ray diffraction, cyclic voltammetry, chronoamperometry, in situ Raman spectroscopy, and X-ray absorption near-edge structure spectroscopy (XANES) were used to investigate the electrochemical oxygen evolution reaction (OER) on Cu, Cu2O, Cu(OH)2, and CuO catalysts. Aqueous 0.1 M KOH was used as the electrolyte. All four catalysts were oxidized or converted to CuO and Cu(OH)2 during a slow anodic sweep of cyclic voltammetry and exhibited similar activities for the OER. A Raman peak at 603 cm–1 appeared for all the four samples at OER-relevant potentials, ≥1.62 V vs RHE. This peak was identified as the Cu–O stretching vibration band of a CuIII oxide, a metastable species whose existence is dependent on the applied potential. Since this frequency matches well with that from a NaCuIIIO2 standard, we suggest that the chemical composition of the CuIII oxide is CuO2–-like. The four catalysts, in stark contrast, did not oxidize the same way during direct chronoamperometry measurements at 1.7 V vs RHE. CuIII oxide was observed only on the CuO and Cu(OH)2 electrodes. Interestingly, these two electrodes catalyzed the OER ∼10 times more efficiently than the Cu and Cu2O catalysts. By correlating the intensity of the Raman band of CuIII oxide and the extent of the OER activity, we propose that CuIII species provides catalytically active sites for the electrochemical water oxidation. The formation of CuIII oxides on CuO films during OER was also corroborated by in situ XANES measurements of the Cu K-edge. The catalytic role of CuIII oxide in the O2 evolution reaction is proposed and discussed.

Hydrogen production via electrochemical water splitting is a promising approach for storing solar energy. For this technology to be economically competitive, it is critical to develop water splitting systems with high solar-to-hydrogen (STH) efficiencies. Here we report a photovoltaic-electrolysis system with the highest STH efficiency for any water splitting technology to date, to the best of our knowledge. Our system consists of two polymer electrolyte membrane electrolysers in series with one InGaP/GaAs/GaInNAsSb triple-junction solar cell, which produces a large-enough voltage to drive both electrolysers with no additional energy input. The solar concentration is adjusted such that the maximum power point of the photovoltaic is well matched to the operating capacity of the electrolysers to optimize the system efficiency. The system achieves a 48-h average STH efficiency of 30%. These results demonstrate the potential of photovoltaic-electrolysis systems for cost-effective solar energy storage.

We report the largely improved electrochemical capacitance of polypyrrole-derived microporous carbon nanospheres (MCNs, 80–100 nm in diameter) containing nitrogen functional groups. We have investigated the electrochemical properties of precursor polypyrrole nanospheres (PNs, with a high N/C ratio and low surface area) and as-derived carbon nanospheres (CNs, with a moderate N/C ratio and low surface area) prepared by carbonizing PNs at different temperatures, and MCNs (with a low N/C ratio and high surface area) obtained by chemical activation of CNs. The samples are thoroughly characterized by transmission electron microscopy (TEM), X-ray diffraction (XRD), Raman spectroscopy, thermogravimetric analysis (TGA), nitrogen sorption, elemental analysis, and X-ray photoelectron spectroscopy (XPS). It is found that MCNs with a high surface area and N-doping species exhibit much better capacitive performance compared to the PNs and CNs, and commercial carbon blacks (XC-72 and BP2000) as well. The MCN sample gives a reversible specific capacitance of ∼240 F g−1 for 3000 cycles in aqueous media as a result of combined advantages of high electrochemical activity of doped heteroatoms (N and O) and accessible well-developed porosity, demonstrating the promising use in high-energy-density supercapacitors.

The recent progress, challenges and promising future on design, synthesis and fabrication of MnO₂for supercapacitors are reviewed and discussed.

We report ferromagnetism in carbon-doped ZnO. Our first-principles calculations based on density functional theory predicted a magnetic moment of 2.02 mu(B) per carbon when carbon substitutes oxygen in ZnO, and an ferromagnetic coupling among magnetic moments of the carbon dopants. The theoretical prediction was confirmed experimentally. C-doped ZnO films deposited by pulsed-laser deposition showed ferromagnetism with Curie temperatures higher than 400 K. The measured magnetic moment based on the content of carbide in the films [(1.5-3.0) mu(B) per carbon] was in agreement with the theoretical prediction. The magnetism is due to the Zn-C system in the ZnO environment.

As an electrical energy storage device, supercapacitor finds attractive applications in consumer electronic products and alternative power source due to its higher energy density, fast discharge/charge time, low level of heating, safety, long-term operation stability, and no disposable parts. This work reviews the recent development of supercapacitor based on carbon nanotubes (CNTs) and their composites. The purpose is to give a comprehensive understanding of the advantages and disadvantages of carbon nanotubes-related supercapacitor materials and to find ways for the improvement in the performance of supercapacitor. We first discussed the effects of physical and chemical properties of pure carbon nanotubes, including size, purity, defect, shape, functionalization, and annealing, on the supercapacitance. The composites, including CNTs/oxide and CNTs/polymer, were further discussed to enhance the supercapacitance and keep the stability of the supercapacitor by optimally engineering the composition, particle size, and coverage.

Fe3O4 has long been regarded as a promising anode material for lithium ion battery due to its high theoretical capacity, earth abundance, low cost, and nontoxic properties. However, up to now no effective and scalable method has been realized to overcome the bottleneck of poor cyclability and low rate capability. In this article, we report a bottom-up strategy assisted by atomic layer deposition to graft bicontinuous mesoporous nanostructure Fe3O4 onto three-dimensional graphene foams and directly use the composite as the lithium ion battery anode. This electrode exhibits high reversible capacity and fast charging and discharging capability. A high capacity of 785 mAh/g is achieved at 1C rate and is maintained without decay up to 500 cycles. Moreover, the rate of up to 60C is also demonstrated, rendering a fast discharge potential. To our knowledge, this is the best reported rate performance for Fe3O4 in lithium ion battery to date.

Abstract A major limitation of MnO 2 in aqueous Zn/MnO 2 ion battery applications is the poor utilization of its electrochemical active surface area. Herein, it is shown that by generating oxygen vacancies ( V O ) in the MnO 2 lattice, Gibbs free energy of Zn 2+ adsorption in the vicinity of V O can be reduced to thermoneutral value (≈0.05 eV). This suggests that Zn 2+ adsorption/desorption process on oxygen‐deficient MnO 2 is more reversible as compared to pristine MnO 2 . In addition, because of the fact that fewer electrons are needed for ZnO bonding in oxygen‐deficient MnO 2 , more valence electrons can be contributed into the delocalized electron cloud of the material, which aids in enhancing the attainable capacity. As a result, the stable Zn/oxygen‐deficient MnO 2 battery is able to deliver one of the highest capacities of 345 mAh g −1 reported for a birnessite MnO 2 system. This excellent electrochemical performance suggests that generating oxygen vacancies in MnO 2 may aid in the future development of advanced cathodes for aqueous Zn ion batteries.

The electrocatalytic reduction of CO2 into value-added chemicals such as hydrocarbons has the potential for supplying fuel energy and reducing environmental hazards, while the accurate tuning of electrocatalysts at the ultimate single-atomic level remains extremely challenging. In this work, we demonstrate an atomic design of multiple oxygen vacancy-bound, single-atomic Cu-substituted CeO2 to optimize the CO2 electrocatalytic reduction to CH4. We carried out theoretical calculations to predict that the single-atomic Cu substitution in CeO2(110) surface can stably enrich up to three oxygen vacancies around each Cu site, yielding a highly effective catalytic center for CO2 adsorption and activation. This theoretical prediction is consistent with our controlled synthesis of the Cu-doped, mesoporous CeO2 nanorods. Structural characterizations indicate that the low concentration (<5%) Cu species in CeO2 nanorods are highly dispersed at single-atomic level with an unconventionally low coordination number ∼5, suggesting the direct association of 3 oxygen vacancies with each Cu ion on surfaces. This multiple oxygen vacancy-bound, single atomic Cu-substituted CeO2 enables an excellent electrocatalytic selectivity in reducing CO2 to methane with a faradaic efficiency as high as 58%, suggesting strong capabilities of rational design of electrocatalyst active centers for boosting activity and selectivity.

The electron-transfer process during the oxygen evolution reaction (OER) often either proceeds solely via a metal redox chemistry (adsorbate evolution mechanism (AEM), with metal bands around the Fermi level) or an oxygen redox chemistry (lattice oxygen oxidation mechanism (LOM), with oxygen bands around the Fermi level). Unlike the AEM, the LOM involves oxygen redox chemistry instead of metal redox, which leads to the formation of a direct oxygen-oxygen (OO) bond. As a result, such a process is able to bypass the rate-determining step, that is, OO bonding, in AEM, which highlights the critical advantage of LOM as compared to the conventional AEM. Thus, it has been well reported that LOM-based catalysts are able to demonstrate higher OER activities as compared to AEM-based catalysts. Here, a comprehensive understanding of the oxygen redox in LOM and all documented and possible characterization techniques that can be used to identify the oxygen redox are reviewed. This review will interpret the origins of oxygen redox in the reported LOM-based electrocatalysts and the underlying science of LOM-induced surface reconstruction in transition metal oxides. Finally, perspectives on the future development of LOM electrocatalysts are also provided.

On the basis of the classical Z-source inverter, this paper presents a developed impedance-type power inverter that is termed the switched inductor (SL) Z-source inverter. To enlarge voltage adjustability, the proposed inverter employs a unique SL impedance network to couple the main circuit and the power source. Compared with the classical Z-source inverter, the proposed inverter increases the voltage boost inversion ability significantly. Only a very short shoot-through zero state is required to obtain high voltage conversion ratios, which is beneficial for improving the output power quality of the main circuit. In addition, the voltage buck inversion ability is also provided in the proposed inverter for those applications that need low ac voltages. Similar to the classical Z-source inverter, the proposed concepts of SL Z-source inverter can be applied to various applications of dc–ac, ac–ac, dc–dc, and ac–dc power conversion. A detailed topology analysis and a generalized discussion are given. Both simulation and experimental results verify the analytical results.

In this tutorial review, recent advances in the synthesis of cyclopropane-containing natural products are discussed, highlighting the application of novel synthetic methodologies and innovative synthetic strategies in the construction of highly functionalized cyclopropanes. The examples showcased herein aim to inspire students and practitioners of organic synthesis to seek further advances in the chemical synthesis of cyclopropanes, both in the context of target-oriented syntheses and method developments.