Axial Chlorine Induced Electron Delocalization in Atomically Dispersed FeN4 Electrocatalyst for Oxygen Reduction Reaction with Improved Hydrogen Peroxide Tolerance.

Atomically dispersed iron sites on nitrogen-doped carbon (Fe-NC) are the most active Pt-group-metal-free catalysts for oxygen reduction reaction (ORR). However, due to oxidative corrosion and the Fenton reaction, Fe-NC catalysts are insufficiently active and stable. Herein, w e demonstrated that the axial Cl-modified Fe-NC (Cl-Fe-NC) electrocatalyst is active and stable for the ORR in acidic conditions with high H2 O2 tolerance. The Cl-Fe-NC exhibits excellent ORR activity, with a high half-wave potential (E1/2 ) of 0.82 V versus a reversible hydrogen electrode (RHE), comparable to Pt/C (E1/2 = 0.85 V versus RHE) and better than Fe-NC (E1/2 = 0.79 V versus RHE). X-ray absorption spectroscopy analysis confirms that chlorine is axially integrated into the FeN4. More interestingly, compared to Fe-NC, the Fenton reaction is markedly suppressed in Cl-Fe-NC. In situ electrochemical impedance spectroscopy reveals that Cl-Fe-NC provides efficient electron transfer and faster reaction kinetics than Fe-NC. Density functional theory calculations reveal that incorporating Cl into FeN4 can drive the electron density delocalization of the FeN4 site, leading to a moderate adsorption free energy of OH* (∆GOH* ), d-band center, and a high onset potential, and promotes the direct four-electron-transfer ORR with weak H2 O2 binding ability compared to Cl-free FeN4, indicating superior intrinsic ORR activity.

Bandgap Shrinkage and Charge Transfer in 2D Layered SnS2 Doped with V for Photocatalytic Efficiency Improvement.

Effects of electronic and atomic structures of V-doped 2D layered SnS2 are studied using X-ray spectroscopy for the development of photocatalytic/photovoltaic applications. Extended X-ray absorption fine structure measurements at V K-edge reveal the presence of VO and VS bonds which form the intercalation of tetrahedral OVS sites in the van der Waals (vdW) gap of SnS2 layers. X-ray absorption near-edge structure (XANES) reveals not only valence state of V dopant in SnS2 is ≈4+ but also the charge transfer (CT) from V to ligands, supported by V Lα,ß resonant inelastic X-ray scattering. These results suggest V doping produces extra interlayer covalent interactions and additional conducting channels, which increase the electronic conductivity and CT. This gives rapid transport of photo-excited electrons and effective carrier separation in layered SnS2 . Additionally, valence-band photoemission spectra and S K-edge XANES indicate that the density of states near/at valence-band maximum is shifted to lower binding energy in V-doped SnS2 compare to pristine SnS2 and exhibits band gap shrinkage. These findings support first-principles density functional theory calculations of the interstitially tetrahedral OVS site intercalated in the vdW gap, highlighting the CT from V to ligands in V-doped SnS2 .

Synergistic Dual-Atom Molecular Catalyst Derived from Low-Temperature Pyrolyzed Heterobimetallic Macrocycle-N4 Corrole Complex for Oxygen Reduction.

A heterobimetallic corrole complex, comprising oxygen reduction reaction (ORR) active non-precious metals Co and Fe with a corrole-N4 center (PhFCC), is successfully synthesized and used to prepare a dual-atom molecular catalyst (DAMC) through subsequent low-temperature pyrolysis. This low-temperature pyrolyzed electrocatalyst exhibited impressive ORR performance, with onset potentials of 0.86 and 0.94 V, and half-wave potentials of 0.75 and 0.85 V, under acidic and basic conditions, respectively. During potential cycling, this DAMC displayed half-wave potential losses of only 25 and 5 mV under acidic and alkaline conditions after 3000 cycles, respectively, demonstrating its excellent stability. Single-cell Nafion-based proton exchange membrane fuel cell performance using this DAMC as the cathode catalyst showed a maximum power density of 225 mW cm-2 , almost close to that of most metal-N4 macrocycle-based catalysts. The present study showed that preservation of the defined CoN4 structure along with the cocatalytic Fe-Cx site synergistically acted as a dual ORR active center to boost overall ORR performance. The development of DAMC from a heterobimetallic CoN4-macrocyclic system using low-temperature pyrolysis is also advantageous for practical applications.

Ni-Nanocluster Modified Black TiO2 with Dual Active Sites for Selective Photocatalytic CO2 Reduction.

One of the key challenges in artificial photosynthesis is to design a photocatalyst that can bind and activate the CO2 molecule with the smallest possible activation energy and produce selective hydrocarbon products. In this contribution, a combined experimental and computational study on Ni-nanocluster loaded black TiO2 (Ni/TiO2[Vo] ) with built-in dual active sites for selective photocatalytic CO2 conversion is reported. The findings reveal that the synergistic effects of deliberately induced Ni nanoclusters and oxygen vacancies provide (1) energetically stable CO2 binding sites with the lowest activation energy (0.08 eV), (2) highly reactive sites, (3) a fast electron transfer pathway, and (4) enhanced light harvesting by lowering the bandgap. The Ni/TiO2[Vo] photocatalyst has demonstrated highly selective and enhanced photocatalytic activity of more than 18 times higher solar fuel production than the commercial TiO2 (P-25). An insight into the mechanisms of interfacial charge transfer and product formation is explored.

Highly efficient visible light photocatalytic reduction of CO2 to hydrocarbon fuels by Cu-nanoparticle decorated graphene oxide.

The production of renewable solar fuel through CO2 photoreduction, namely artificial photosynthesis, has gained tremendous attention in recent times due to the limited availability of fossil-fuel resources and global climate change caused by rising anthropogenic CO2 in the atmosphere. In this study, graphene oxide (GO) decorated with copper nanoparticles (Cu-NPs), hereafter referred to as Cu/GO, has been used to enhance photocatalytic CO2 reduction under visible-light. A rapid one-pot microwave process was used to prepare the Cu/GO hybrids with various Cu contents. The attributes of metallic copper nanoparticles (∼4-5 nm in size) in the GO hybrid are shown to significantly enhance the photocatalytic activity of GO, primarily through the suppression of electron-hole pair recombination, further reduction of GO's bandgap, and modification of its work function. X-ray photoemission spectroscopy studies indicate a charge transfer from GO to Cu. A strong interaction is observed between the metal content of the Cu/GO hybrids and the rates of formation and selectivity of the products. A factor of greater than 60 times enhancement in CO2 to fuel catalytic efficiency has been demonstrated using Cu/GO-2 (10 wt % Cu) compared with that using pristine GO.

Development of a Lightweight LTO/Cu Electrode as a Flexible Anode via Etching Process for Lithium-Ion Batteries.

In recent years, flexible energy storage devices have attracted the growing demand for flexible electronic systems. Therefore, research on reliable electrodes with high mechanical flexibility and good electronic and lithium-ion conductivity has become critical. Carbon-coated Li4Ti5O12 (LTO) nanostructures find essential applications in high-performance lithium-ion batteries (LiBs). Nevertheless, the conventional copper current collector with a thickness of several micrometers accounts for a large proportion of the LiB, making the low-energy density LiB with much less flexibility. Here, hundred nm-thick (LTO/Cu) copper foil-LTO nanostructures are fabricated using a scalable and straightforward process which can be assembled into a film into a flexible, lightweight electrode by etching a conventional copper foil to form an ultra-thin copper layer for LIBs (<1 µm). This process provides essential flexibility to the as-prepared electrode and provides template support for simple fabrication. The LiB cell using the novel LTO/Cu as the anode exhibits an energy capacity of 123 mA h/g during 40 charge-discharge cycles at a 0.1C rate. Besides, the coulombic efficiency of the LiB using LTO/Cu remains over 99% after 40 cycles. These results show the uses of this novel anode and its potential in high-density and flexible commercial lithium-ion batteries.

Simple way of making free-standing cathode electrodes for flexible lithium-ion batteries.

The flexible electrodes used in the lithium-ion battery (LIB) offer an excellent opportunity to be bent and folded without deforming their electrochemical characteristics. However, a flexible electrode does not include metal foil as a current collector, limiting the LIB's flexibility and weakening the mechanical strength. This study fabricates flexible LiFePO4 (LFP) free-standing electrodes by a scalable and straightforward solution-based etching process. The obtained free-standing electrodes show capacities and bending performances that are similar to the conventional electrodes with aluminum current collectors. This study opens a new avenue for developing a free-standing electrode for low-cost and flexible lithium-ion batteries.

Atomistic insights into highly active reconstructed edges of monolayer 2H-WSe2 photocatalyst.

Ascertaining the function of in-plane intrinsic defects and edge atoms is necessary for developing efficient low-dimensional photocatalysts. We report the wireless photocatalytic CO2 reduction to CH4 over reconstructed edge atoms of monolayer 2H-WSe2 artificial leaves. Our first-principles calculations demonstrate that reconstructed and imperfect edge configurations enable CO2 binding to form linear and bent molecules. Experimental results show that the solar-to-fuel quantum efficiency is a reciprocal function of the flake size. It also indicates that the consumed electron rate per edge atom is two orders of magnitude larger than the in-plane intrinsic defects. Further, nanoscale redox mapping at the monolayer WSe2-liquid interface confirms that the edge is the most preferred region for charge transfer. Our results pave the way for designing a new class of monolayer transition metal dichalcogenides with reconstructed edges as a non-precious co-catalyst for wired or wireless hydrogen evolution or CO2 reduction reactions.

Enhancing the Areal Capacity and Stability of Cu2ZnSnS4 Anode Materials by Carbon Coating: Mechanistic and Structural Studies During Lithiation and Delithiation.

The widespread use of energy storage technologies has created a high demand for the development of novel anode materials in Li-ion batteries (LIBs) with high areal capacity and faster electron-transfer kinetics. In this work, carbon-coated Cu2ZnSnS4 with a hierarchical 3D structure (CZTS@C) is used as an anode material for LIBs. The CZTS@C microstructures with enhanced electrical conductivity and improved Li-ion diffusivity exhibit high areal and gravimetric capacities of 2.45 mA h/cm2 and 1366 mA h/g, respectively. The areal capacity achieved in the present study is higher than that of previously reported CZTS-based materials. Moreover, in situ X-ray diffraction results show that lithium ions are stored in CZTS through the insertion reaction, followed by the alloying and conversion reactions at ∼1 V. The structural evolution of Li2S and Cu-Sn/Cu-Zn alloy phases occurs during the conversion and alloying reactions. The present work provides a cost-effective and simple method to prepare bulk CZTS and highlights the conformal carbon coating over CZTS, which can enhance the electrical and ionic conductivities of CZTS materials and increase the mass loading (1-2.3 mg/cm2). The improved stability and rate capability of CZTS@C anode materials can therefore be achieved.

Synthesis and characterization of "hairy urchin"-like polyaniline by using ß-cyclodextrin as a template.

A novel synthesis of "hairy urchin"-shaped polyaniline (PAni) and its surface coverage with nanospikes was achieved from a simple microemulsion polymerization technique in the presence of ß-cyclodextrin (ß-CD). The rodlike micelle phase was characterized, and the key factors affecting the formation of PAni nanostructures were systematically examined. Ferric chloride (FeCl(3)) has played a role as a structural directing agent to fabricate the polymer as hairy urchin-like structure/nanorods via a cooperative interaction between FeCl(3) and DoTAC in an aqueous medium. Host-guest inclusion complex of ß-cyclodextrin with aniline was used as a monomer. It has been revealed that the formation of the supramolecular complexes of polyaniline with ß-CD due to host-guest interaction is indispensable for the fabrication of these unique PAni nanostructures, and a suitable ß-CD to aniline molar ratio is essential to their exclusive formation. Different varieties of PAni nanostructures such as hairy urchin, branched particles consisting of rodlike branches, and regular rodlike particles were obtained in the presence of FeCl(3). Also, in the absence of FeCl(3), a predominant product of regular spherical particles and wirelike aggregation exhibiting faceted surfaces were obtained. The structures of polyaniline hairy urchin-like nanorods were analyzed using transmission electron microscopy (TEM). The synthesized polymer was characterized by Fourier-transform infrared spectroscopy and X-ray diffraction technique. Additionally, the relationship between the morphology and the conductivity of the PAni nanostructures was investigated as well.

Synthesis of beta-cyclodextrin-modified water-dispersible Ag-TiO2 core-shell nanoparticles and their photocatalytic activity.

The beta-cyclodextrin-modified Ag-TiO2 core-shell nanoparticles were prepared by sodium borohydrate reduction of AgNO3 and the subsequent hydrolysis of the tetraisopropyl orthotitanate in an aqueous medium. Inversely in the preparation of beta-cyclodextrin-modified TiO2-Ag core-shell nanoparticles, first hydrolysis and then following reduction were carried out. The synthesized spherical core-shell nanoparticles were highly water-dispersible and had an average diameter in the range of 9 to 12 nm. A significant shifting of surface plasmon band was observed for the synthesized Ag-TiO2 and TiO2-Ag core-shell nanoparticles. On a model reaction, namely, the photodegradation of phenol by the UV light irradiation, the photocatalytic property of TiO2 nanoparticles was enhanced, when the Ag nanoparticle was embedded in the core of TiO2 nanoparticles but TiO2 nanoparticles coated by Ag shell decreased the photocatalytic property of TiO2 nanoparticles. The mechanism is ascribed to the surface plasmon characteristics of Ag in the core of the TiO2 nanoparticles under the acceleration by host-guest inclusion characteristics.

Integrated nano-architectured photocatalysts for photochemical CO2 reduction.

Recent advances in nanotechnology, especially the development of integrated nanostructured materials, have offered unprecedented opportunities for photocatalytic CO2 reduction. Compared to bulk semiconductor photocatalysts, most of these nanostructured photocatalysts offer at least one advantage in areas such as photogenerated carrier kinetics, light absorption, and active surface area, supporting improved photochemical reaction efficiencies. In this review, we briefly cover the cutting-edge research activities in the area of integrated nanostructured catalysts for photochemical CO2 reduction, including aqueous and gas-phase reactions. Primarily explored are the basic principles of tailor-made nanostructured composite photocatalysts and how nanostructuring influences photochemical performance. Specifically, we summarize the recent developments related to integrated nanostructured materials for photocatalytic CO2 reduction, mainly in the following five categories: carbon-based nano-architectures, metal-organic frameworks, covalent-organic frameworks, conjugated porous polymers, and layered double hydroxide-based inorganic hybrids. Besides the technical aspects of nanostructure-enhanced catalytic performance in photochemical CO2 reduction, some future research trends and promising strategies are addressed.

Realizing Catalytic Acetophenone Hydrodeoxygenation with Palladium-Equipped Porous Organic Polymers.

Porous organic polymers (POPs) constructed through covalent bonds have raised tremendous research interest because of their suitability to develop robust catalysts and their successful production with improved efficiency. In this work, we have designed and explored the properties and catalytic activity of a template-free-constructed, hydroxy (-OH) group-enriched porous organic polymer (Ph-POP) bearing functional Pd nanoparticles (Pd-NPs) by one-pot condensation of phloroglucinol (1,3,5-trihydroxybenzene) and terephthalaldehyde followed by solid-phase reduction with H2. The encapsulated Pd-NPs rested within well-defined POP nanocages and remained undisturbed from aggregation and leaching. This polymer hybrid nanocage Pd@Ph-POP is found to enable efficient liquid-phase hydrodeoxygenation (HDO) of acetophenone (AP) with high selectivity (99%) of ethylbenzene (EB) and better activity than its Pd@Al2O3 counterpart. Our investigation demonstrates a facile, scalable, catalyst-template-free methodology for developing novel porous organic polymer catalysts and next-generation efficient greener chemical processes from platform molecules to produce value-added chemicals. With the aid of comprehensive in situ ATR-IR spectroscopy experiments, it is suggested that EB can be more easily desorbed in a solution, reflecting from the much weaker but better-resolved signal at 1494 cm-1 in Pd@Ph-POP compared to that in Pd@Al2O3, which is the key determining factor in favoring an efficient catalytic mechanism. Density functional theory (DFT) calculations were performed to illustrate the detailed reaction network and explain the high catalytic activity observed for the fabricated Pd@Ph-POP catalyst in the HDO conversion of AP to EB. All of the hydrogenation routes, including direct hydrogenation by surface hydrogen, hydrogen transfer, and the keto-enol pathway, are evaluated, providing insights into the experimental observations. The presence of phenolic hydroxyl groups in the Ph-POP frame structure facilitates the hydrogen-shuttling mechanism for dehydration from the intermediate phenylethanol, which was identified as a crucial step for the formation of the final product ethylbenzene. Besides, weaker binding of the desired product ethylbenzene and lower coverage of surface hydrogen atoms on Pd@Ph-POP both contributed to inhibiting the overhydrogenation reaction and explained well the high yield of EB produced during the HDO conversion of AP on Pd@Ph-POP in this study.

KSCN-induced Interfacial Dipole in Black TiO2 for Enhanced Photocatalytic CO2 Reduction.

Tuning the electronic band structure of black titania to improve photocatalytic performance through conventional band engineering methods has been challenging because of the defect-induced charge carrier and trapping sites. In this study, KSCN-modified hydrogenated nickel nanocluster-modified black TiO2 (SCN-H-Ni-TiO2) exhibits enhanced photocatalytic CO2 reduction due to the interfacial dipole effect. Upon combining the experimental and theoretical simulation approach, the presence of an electrostatic interfacial dipole associated with chemisorption of SCN has dramatic effects on the photocatalyst band structure in SCN-H-Ni-TiO2. An interfacial dipole possesses a more negative zeta potential shift of the isoelectric point from 5.20 to 3.20, which will accelerate the charge carrier separation and electron transfer process. Thiocyanate ion passivation on black TiO2 demonstrated an increased work function around 0.60 eV, which was induced by the interracial dipole effect. Overall, the SCN-H-Ni-TiO2 photocatalyst showed an enhanced CO2 reduction to solar fuel yield by 2.80 times higher than H-Ni-TiO2 and retained around 88% product formation yield after 40 h.

Carbon-doped SnS2 nanostructure as a high-efficiency solar fuel catalyst under visible light.

Photocatalytic formation of hydrocarbons using solar energy via artificial photosynthesis is a highly desirable renewable-energy source for replacing conventional fossil fuels. Using an L-cysteine-based hydrothermal process, here we synthesize a carbon-doped SnS2 (SnS2-C) metal dichalcogenide nanostructure, which exhibits a highly active and selective photocatalytic conversion of CO2 to hydrocarbons under visible-light. The interstitial carbon doping induced microstrain in the SnS2 lattice, resulting in different photophysical properties as compared with undoped SnS2. This SnS2-C photocatalyst significantly enhances the CO2 reduction activity under visible light, attaining a photochemical quantum efficiency of above 0.7%. The SnS2-C photocatalyst represents an important contribution towards high quantum efficiency artificial photosynthesis based on gas phase photocatalytic CO2 reduction under visible light, where the in situ carbon-doped SnS2 nanostructure improves the stability and the light harvesting and charge separation efficiency, and significantly enhances the photocatalytic activity.

Directly-Grown Hierarchical Carbon Nanotube@Polypyrrole Core-Shell Hybrid for High-Performance Flexible Supercapacitors.

A hierarchical carbon nanotube-polypyrrole (CNT-PPy) core-shell composite was fabricated by growing CNTs directly on carbon cloth (CC) as a skeleton followed by electropolymerization of PPy with controlled polymerization time. Direct fabrication of electroactive (CNT-PPy) materials on the flexible CC electrode could reduce the interfacial resistance between the electrode and electrolyte and improve the ion diffusion. The supercapacitor electrode based on optimized PPy/CNT-CC exhibits excellent electrochemical performance, with the highest gravimetric capacitance being roughly 1038 F g(-1) per active mass of PPy and up to 486.1 F g(-1) per active mass of the PPy/CNT composite. Notably, excellent flexibility and cycle stability up to 10 000 cycles with only 18 % capacitance loss was achieved. At the same time, the fabricated asymmetric supercapacitor (PPy/CNT-CC∥CNT-CC) shows the maximum power density of 10 962 W kg(-1) at an energy density of 3.9 Wh kg(-1) under the operating potential of 1.4 V. The overall high cycle stability and high performance of the fabricated PPy/CNT-CC flexible electrode is due to the novel binder-free direct growth process.

Graphene oxide as a promising photocatalyst for CO2 to methanol conversion.

Photocatalytic conversion of carbon dioxide (CO(2)) to hydrocarbons such as methanol makes possible simultaneous solar energy harvesting and CO(2) reduction, two birds with one stone for the energy and environmental issues. This work describes a high photocatalytic conversion of CO(2) to methanol using graphene oxides (GOs) as a promising photocatalyst. The modified Hummer's method has been applied to synthesize the GO based photocatalyst for the enhanced catalytic activity. The photocatalytic CO(2) to methanol conversion rate on modified graphene oxide (GO-3) is 0.172 µmol g cat(-1) h(-1) under visible light, which is six-fold higher than the pure TiO(2).

Sensitizing of pyrene fluorescence by ß-cyclodextrin-modified TiO2 nanoparticles.

TiO(2) nanoparticles were synthesized by hydrolysis of tetraisopropyl orthotitanate in an aqueous solution of cyclodextrin. The ß-cyclodextrin-modified spherical TiO(2) nanoparticles were water-dispersible and had an average particle diameter of 4.4 ± 1 nm. Pyrene fluorescence was enhanced by increasing the concentration of ß-cyclodextrin-modified TiO(2) nanoparticle and the sensitization effect was triply stronger than the case of the ß-cyclodextrin only. The increase in a concentration of host (ß-cyclodextrin) changes its microenvironment for guest (pyrene), that is, the interaction of pyrene with apolar cavity of ß-cyclodextrin increases, resulting in enhancement of fluorescence. The sensitization behavior of pyrene fluorescence in the presence of TiO(2) nanoparticles occurs from the increase in the extinction coefficient of pyrene, demonstrating the charge transfer between pyrene and metal oxide nanoparticle.