Evolution Mechanism of Solid-Phase Catalysts During Catalytic Growth of Single-Walled Carbon Nanotubes.

Using solid nanoparticles (NPs) as catalysts is the most effective method to achieve catalytic growth of single-walled carbon nanotubes (SWCNTs) with ultrapure chirality. Until now, SWCNTs with a suitable chirality purity have not been prepared in experiments. That is, the evolution of solid NPs during the catalytic growth of SWCNTs is in contradiction with the original concept of a changeless structure. Hence, in this work, the evolution mechanism of solid cobalt NPs during the nucleation process of SWCNTs is analyzed through molecular dynamics. Similar to the experimental observations, the results show that a drastic structural fluctuation of the NPs occurs during the nucleation of SWCNTs. This structural fluctuation is caused by the fact that the elastic strain energy and surface energy of the NPs can be tuned when a carbon gradient exists between the subsurface and interior of the NP. Furthermore, such a carbon gradient can be reduced by changing the carbon feeding rate. This work not only reveals the evolution mechanism of solid catalysts during the nucleation of SWCNTs but also provides prospects for realizing solid catalysts with a changeless structure by tuning the experimental parameters.

Single Transition-Metal Atom Anchored on a Rhenium Disulfide Monolayer: An Efficient Bifunctional Electrocatalyst for the Oxygen Evolution and Oxygen Reduction Reactions.

Developing efficient oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) bifunctional electrocatalysts is attractive for rechargeable metal-air batteries. Meanwhile, single metal atoms embedded in 2D layered transition metal chalcogenides (TMDs) have become a very promising catalyst. Recently, many attentions have been paid to the 2D ReS2 electrocatalyst due to its unique distorted octahedral 1T' crystal structure and thickness-independent electronic properties. Here, the catalytic activity of different transition metal (TM) atoms embedded in ReS2 using the density functional theory is investigated. The results indicate that TM@ReS2 exhibits outstanding thermal stability, good electrical conductivity, and electron transfer for electrochemical reactions. And the Ir@ReS2 and Pd@ReS2 can be used as OER/ORR bifunctional electrocatalysts with a lower overpotential for OER (ηOER) of 0.44 V and overpotentials for ORR (ηORR) of 0.26 V and 0.27 V, respectively. The excellent catalytic activity is attributed to the optimal adsorption strength for oxygen intermediates coming from the effective modulation of the electronic structure of ReS2 after Ir/Pd doping. The results can help to deeply understand the catalytic activity of TM@ReS2 and develop novel and highly efficient OER/ORR electrocatalysts.

The enhanced bandgap and birefringence of rare-earth phosphates XPO4 (X = Sc, Y, La, and Lu): a first-principles investigation.

Rare-earth phosphates were thought to be good candidates as ultraviolet/deep ultraviolet optical materials due to their relatively large bandgap and optical properties. In this paper, the authors screened out a family of XPO4 (X = Sc, Y, La, and Lu) compounds with an enhanced bandgap (HSE06 bandgap ≥ 7.61 eV) and birefringence (0.0934-0.2003@1064 nm) using first-principles calculations. The origin of enhanced optical properties was investigated using projected density of states, distortion indices, and Born effective charges. The results show that the PO4 anionic groups and X-O polyhedra give the main contribution in determining the optical properties, and the PO4 anionic groups give more contribution than other functional basic units. The spin-orbit interaction was also investigated. Similar band structures were found after spin-orbit coupling (SOC) was considered, and slightly enhanced birefringence was found when SOC was applied to these rare-earth phosphates.

A TD-DFT study of a class of D-π-A fluorescent probes for detection of typical oxidants.

A deep understanding of the fluorescence response mechanisms is the foundation for design-oriented strategies for D-π-A probes for trace hazardous chemicals. Here, from the perspective of electronegativity regulation of the π-bridge recognition site, an electron-donation modulation strategy involving various comprehensive evaluations of the optical and chemical properties is proposed through a series of theoretical analyses. Due to the preferential combined interaction between the π-bridge recognition site and MnO4-, high electrophilic reactivity and feasible chemical reaction energy barrier, a high-performance filter paper chip and hydrogel chip for the detection of aqueous and air-suspended environmental KMnO4 was achieved. We expect the present modulation strategy will facilitate efficient fluorescent probe design and provide a universal methodology for the exploration of functional D-π-A molecules.

Combined piezoelectricity, valley splitting and Dzyaloshinskii-Moriya interaction in Janus GdXY (X, Y = Cl, Br, I) magnetic semiconductors.

Janus materials, as a family of multifunctional materials with broken mirror symmetry, have played a great role in piezoelectric, valley-related, and Rashba spin-orbit coupling (SOC) applications. Using first-principles calculations, it is predicted that monolayer 2H-GdXY (X, Y = Cl, Br, I) will combine giant piezoelectricity, intrinsic valley splitting and a strong Dzyaloshinskii-Moriya interaction (DMI), resulting from the intrinsic electric polarization, spontaneous spin polarization and strong spin-orbit coupling. Opposite Berry curvatures and unequal Hall conductivities at the K- and K'-valleys of monolayer GdXY are promising for storing information through the anomalous valley Hall effect (AVHE). Through construction of the spin Hamiltonian and micromagnetic model, we obtained the primary magnetic parameters of monolayer GdXY as a function of the biaxial strain. Due to the dimensionless parameter κ having strong tunability, monolayer GdClBr is promising to host isolated skyrmions. The present results are expected to enable the application of Janus materials in piezoelectricity, spin- and valley-tronics and the formation of chiral magnetic structures.

A Deep Understanding on the Effective Generation of Twisted Intramolecular Charge Transfer by Protonation in Thiazolo[5,4-d]thiazole Derivatives.

The exploration of the intrinsic relationship between the phototautomerization and photoelectric properties is of great significance for the application of the emerging novel organic materials, such as the (bi)heterocyclic thiazolo[5,4-d]thiazole derivatives (TzTz). Here, by introducing the chemical-controlling protonation, a barrierless spontaneous rotation movement of the designed TzTz derivative (2,5-diyl-amino-thiazolo[5,4-d]thiazole, DA-TzTz) was ensured through the facilitation of the excited-state intramolecular proton transfer (ESIPT) triggered twisted intramolecular charge transfer (TICT) process by the enhancement of the intramolecular hydrogen bonds, steric hindrance effect, and conjugative effect. It is further verified that the hetero S atoms could mostly effect the proton accepting ability of -N═ through comparing with the influences to the intramolecular H-bond between the protonated/nonprotonated amino groups and the -N═ atoms brought by the replacement of them with N or O atoms. As a result, the dissociation and rearrangement of the π conjugation in DA-TzTz accompanying with the variation of the optoelectronic characteristics was benefited from the establishment of the preferential charge-transfer and separation. We expect this tentative study could establish a new concept of designing an efficient charge-transfer and separation method, paving the way for the development of the TzTz derivatives and other optoelectronic organic materials.

A Theoretical Perspective to Study the Optical Properties of Tetrafluoroborates.

In this study, a series of tetrafluoroborates with non-π-conjugated [BF4 ] tetrahedra are investigated systematically by first-principles calculations. Theoretical studies demonstrate that tetrafluoroborates with alkali and/or alkaline-earth metals are more favorable for deep-ultraviolet transmission and are comparable to the classical deep-ultraviolet (deep-UV) material, MgF2 . Furthermore, bandgap decrease with the increasing of ionic radii in alkali and/or alkaline-earth metals. Introducing highly polarizable cations with d10 -configuration or cations with lone pair electrons into the structure will decrease the bandgaps. The birefringence and second harmonic generation effects are not large enough in tetrafluoroborates because polarizability anisotropy and hyperpolarizability in non-π-conjugated [BF4 ] tetrahedra are much smaller than those in π-conjugated groups. However, the second harmonic generation effect for [BF4 ] tetrahedra has a higher contribution in comparison with that due to birefringence. To effectively synthesize the borate fluorides or fluorooxoborates in the deep-UV region, raw materials with B-F bonds are preferred.

The evolution mechanism of an FeMo alloy catalyst for growth of single-walled carbon nanotubes.

Adding small fractions of Mo to Fe nanoparticles (NPs) can reduce the melting point of FeMo NPs to lower than that of Fe NPs to prolong the lifetime of the alloy catalyst which in turn promotes the quality of catalytically synthesized single-walled carbon nanotubes (SWCNTs). In this study, we reveal the mechanism of the above-mentioned abnormal melting behavior by employing molecular dynamics simulations. Our results indicate that the bond length between the Fe atoms and the number of bonds between the Mo atoms play an important role in reducing the melting point of the FeMo NPs. This study provides useful insight into the evolution mechanism of the alloy catalyst for the growth of SWCNTs.

Detection of Triacetone Triperoxide (TATP) Precursors with an Array of Sensors Based on MoS2/RGO Composites.

Triacetone triperoxide (TATP) is a self-made explosive synthesized from the commonly used chemical acetone (C3H6O) and hydrogen peroxide (H2O2). As C3H6O and H2O2 are the precursors of TATP, their detection is very important due to the high risk of the presence of TATP. In order to detect the precursors of TATP effectively, hierarchical molybdenum disulfide/reduced graphene oxide (MoS2/RGO) composites were synthesized by a hydrothermal method, using two-dimensional reduced graphene oxide (RGO) as template. The effects of the ratio of RGO to raw materials for the synthesis of MoS2 on the morphology, structure, and gas sensing properties of the MoS2/RGO composites were studied. It was found that after optimization, the response to 50 ppm of H2O2 vapor was increased from 29.0% to 373.1%, achieving an increase of about 12 times. Meanwhile, all three sensors based on MoS2/RGO composites exhibited excellent anti-interference performance to ozone with strong oxidation. Furthermore, three sensors based on MoS2/RGO composites were fabricated into a simple sensor array, realizing discriminative detection of three target analytes in 14.5 s at room temperature. This work shows that the synergistic effect between two-dimensional RGO and MoS2 provides new possibilities for the development of high performance sensors.

High-Performance Gas Sensor of Polyaniline/Carbon Nanotube Composites Promoted by Interface Engineering.

Inspired by the enhanced gas-sensing performance by the one-dimensional hierarchical structure, one-dimensional hierarchical polyaniline/multi-walled carbon nanotubes (PANI/CNT) fibers were prepared. Interestingly, the simple heating changed the sensing characteristics of PANI from p-type to n-type and n-type PANI and p-type CNTs form p-n hetero junctions at the core-shell interface of hierarchical PANI/CNT composites. The p-type PANI/CNT (p-PANI/CNT) and n-type PANI/CNT (n-PANI/CNT) performed the higher sensitivity to NO2 and NH3, respectively. The response times of p-PANI/CNT and n-PANI/CNT to 50 ppm of NO2 and NH3 are only 5.2 and 1.8 s, respectively, showing the real-time response. The estimated limit of detection for NO2 and NH3 is as low as to 16.7 and 6.4 ppb, respectively. After three months, the responses of p-PANI/CNT and n-PANI/CNT decreased by 19.1% and 11.3%, respectively. It was found that one-dimensional hierarchical structures and the deeper charge depletion layer enhanced by structural changes of PANI contributed to the sensitive and fast responses to NH3 and NO2. The formation process of the hierarchical PANI/CNT fibers, p-n transition, and the enhanced gas-sensing performance were systematically analyzed. This work also predicts the development prospects of cost-effective, high-performance PANI/CNT-based sensors.

Soft Confinement-Induced Morphologies of the Blends of AB Diblock Copolymers and C Homopolymers.

Self-assembly behavior of the blends of AB diblock copolymers and C homopolymers in soft confinement is studied by using a simulated annealing method. Polymer solution droplets in a poor solvent environment realize the soft confinement. Several sequences of soft confinement-induced copolymer aggregates with different shapes and internal structures are predicted as functions of the size of confinement, the number ratio of AB diblock copolymers to C homopolymers, the volume fraction of blocks, the selectivity of confinement's surface, the incompatibility between blocks, and the competition between two block-homopolymer interactions. Simulation results demonstrate that those factors are able to tune the morphology of the aggregates precisely. We anticipate the rules achieved here is helpful to fabrication of polymeric particle with predesigned morphology.

Multichannel Discriminative Detection of Explosive Vapors with an Array of Nanofibrous Membranes Loaded with Quantum Dots.

The multichannel fluorescent sensor array based on nanofibrous membranes loaded with ZnS quantum dots (QDs) was created and demonstrated for the discriminative detection of explosives. The synergistic effect of the high surface-to-volume ratio of QDs, the good permeability of nanofibrous membranes and the differential response introduced by surface ligands was played by constructing the sensing array using nanofibrous membranes loaded with ZnS QDs featuring several surface ligands. Interestingly, although the fluorescence quenching of the nanofibrous membranes is not linearly related to the exposure time, the fingerprint of each explosive at different times is very similar in shape, and the fingerprints of the three explosives show different shapes. Three saturated vapors of nitroaromatic explosives could be reliably detected and discriminated by the array at room temperature. This work is the first step toward devising a monitoring system for explosives in the field of public security and defense. It could, for example, be coupled with the technology of image recognition and large data analysis for a rapid diagnostic test of explosives. This work further highlights the power of differential, multichannel arrays for the rapid and discriminative detection of a wide range of chemicals.

Theoretical simulation of the reduction of graphene oxide by lithium naphthalenide.

Based on density functional theory, we investigated the mechanism of graphene oxide reduction by lithium naphthalenide (C10H8Li). C10H8(-) easily reacts with GO to form a neutral C10H8 and the negatively charged GO, which can attach to Li(+) ions to form lithium oxide on a graphene skeleton. The reduction mechanism is similar to the reduction of GO by metallic Li; the C10H8 is used to disperse Li in THF solution. Furthermore, the lithium oxide on GO can react with CO2 to form Li2CO3 and be further reduced by MeOH washing. In the negatively charged GO, the carboxyl at the edge of GO transfers an electron to GO and releases a CO2 molecule by overcoming a barrier of 0.19 eV. CO2 can also be adsorbed by lithium oxide to form Li2CO3 that is tightly attached on graphene skeleton. After GO is partially reduced, the adsorption of CO2 eliminates O in the form of Li2CO3 without any barrier. This mechanism can be helpful for further understanding the nature of GO reduction among various reducing agents and for exploring new and efficient GO reducing agents.

Theoretical simulation of reduction mechanism of graphene oxide in sodium hydroxide solution.

Based on a density functional theory simulation, we proposed a reduction mechanism of graphene oxide (GO) under a sodium hydroxide solution containing anions (OH(-)), cations (Na(+)) and neutral H2O molecules as main components. OH(-) anion can interact with hydroxyl in GO and transfer electrons to the graphene sheet, resulting in negatively charged GO, and these electrons obviously lower the barrier of the ring-opening reaction of epoxy. Na(+) cations can be attracted by the negatively charged GO, and this reaction is equivalent to the one between metallic Na and GO. The opened epoxy is reduced with the assistance of Na(+) cation and water molecule. In such a reduction process, NaOH can be viewed as a catalyst and more defects should be formed because of these diffused epoxies on the negatively charged graphene sheet. Our results may be helpful to understand further the nature of the reduction of GO among various reducing agents.

The Spin-Orbit Effect on the Electronic Structures, Refractive Indices, and Birefringence of X2PO4I (X = Pb, Sn, Ba and Sr): A First-Principles Investigation.

Introducing post-transition metal cations is an excellent strategy for enhancing optical properties. This paper focuses on four isomers, namely the X2PO4I (X = Pb, Sn, Ba, and Sr) series. For the first time, the paper's attention is paid to the changes in electronic structure, as well as refractive indices and birefringence, with and without the inclusion of spin-orbit effects in this series. The first-principles results show that spin-orbit effects of the 5p and 6p states found in these compounds lead to splitting of the bands, narrowing of the band gap, enhancement of the lone-pair stereochemistry, and enhancement of the refractive indices and birefringence. Moreover, a comparison of the lone-pair electron phosphates, X2PO4I (X = Pb and Sn), and the isomeric alkaline earth metal phosphates, X2PO4I (X = Ba and Sr), reveals that changes in the band structure have a greater effect on the enhancement of the birefringence than the slight enhancement of the lone-pair stereochemical activity. This study has important implications for a deeper understanding of the optical properties of crystals and the design of novel optical materials.

Oxygen vacancy induced interaction between Pt and TiO2 to improve the oxygen reduction performance.

In proton exchange membrane fuel cells (PEMFCS), a Pt-based catalyst has been plagued by activity and durability, making it difficult to implement in large-scale commercial applications. In this paper, a composite material formed by titanium dioxide and carbon black containing oxygen vacancies (TiO2(OV)-C) was used as a functional support to successfully load Pt nanoparticles (NPS). The introduction of oxygen vacancies induces the formation of a connection between Pt and TiO2, which not only strengthens the fixation of Pt by the composite support but also optimizes the local charge density of Pt. Compared with Pt/C (0.842 V) and Pt/TiO2-C (0.841 V), the half-wave potential (E1/2) of Pt/TiO2(OV)-C (0.862 V) is increased by 20 mV and 21 mV, respectively. After a long-term durability test, the E1/2 of Pt/TiO2(OV)-C is only attenuated by 5 mV. In addition, the mass activity (MA) and specific activity (SA) decreased from 183.4 mA mg-1 and 0.565 mA cm-2 to 144.4 mA mg-1 and 0.483 mA cm-2 at 0.85 V, only decreasing by 21% and 17 %, showing good stability. X-ray photoelectron spectroscopies (XPS) and density functional theory (DFT) calculations show that the interaction between Pt and TiO2 reduces the d-band center of Pt, thereby improving the desorption of intermediates *OH, which in turn promotes the activity of alkaline ORR. This study not only shows that OV plays a key role in the process of inducing interaction, but also deeply studies the influence of this interaction on the active site Pt, which provides more choices for the design of excellent multiphase catalysts.

Oxygen Vacancies-Rich S-Cheme BiOBr/CdS Heterojunction with Synergetic Effect for Highly Efficient Light Emitting Diode-Driven Pollutants Degradation.

Recently, the use of semiconductor-based photocatalytic technology as an effective way to mitigate the environmental crisis attracted considerable interest. Here, the S-scheme BiOBr/CdS heterojunction with abundant oxygen vacancies (Vo-BiOBr/CdS) was prepared by the solvothermal method using ethylene glycol as a solvent. The photocatalytic activity of the heterojunction was investigated by degrading rhodamine B (RhB) and methylene blue (MB) under 5 W light-emitting diode (LED) light. Notably, the degradation rate of RhB and MB reached 97% and 93% in 60 min, respectively, which were better than that of BiOBr, CdS, and BiOBr/CdS. It was due to the construction of the heterojunction and the introduction of Vo, which facilitated the spatial separation of carriers and enhanced the visible-light harvest. The radical trapping experiment suggested that superoxide radicals (·O2-) acted as the main active species. Based on valence balance spectra, Mott-Schottky(M-S) spectra, and DFT theoretical calculations, the photocatalytic mechanism of the S-scheme heterojunction was proposed. This research provides a novel strategy for designing efficient photocatalysts by constructing S-scheme heterojunctions and introducing oxygen vacancies for solving environmental pollution.

Synthesis and Sensing Performance of Chitin Fiber/MoS2 Composites.

In this study, chitin fibers (CFs) were combined with molybdenum sulfide (MoS2) to develop high-performance sensors, and chitin carbon materials were innovatively introduced into the application of gas sensing. MoS2/CFs composites were synthesized via a one-step hydrothermal method. The surface properties of the composites were greatly improved, and the fire resistance effect was remarkable compared with that of the chitin monomer. In the gas-sensitive performance test, the overall performance of the MoS2/CFs composite was more than three times better than that of the MoS2 monomer and showed excellent long-term stability, with less than 10% performance degradation in three months. Extending to the field of strain sensing, MoS2/CFs composites can realize real-time signal conversion in tensile and motion performance tests, which can help inspectors make analytical judgments in response to the analysis results. The extensive application of sensing materials in more fields is expected to be further developed. Based on the recycling of waste chitin textile materials, this paper expands the potential applications of chitin materials in the fields of gas monitoring, biomedicine, behavioral discrimination and intelligent monitoring.

Positive and Negative Contribution from Lead-Oxygen Groups and Halogen Atoms to Birefringence: A First Principles Investigation.

Oxyhalides, containing oxygen and halogen atoms and combining the advantages of oxides and halides in geometry and optical response, have great potential in optical materials. In this study, the electronic structures and the optical properties of the Pb3O2X2 (X = Cl, Br, I) compounds have been investigated using the first principles method. The results show that these compounds have birefringence at 0.076, 0.078, and 0.059 @ 1064 nm, respectively. And, the asymmetric stereochemical active lone pair electrons were found around lead atoms, which were confirmed by the projected density of states, the electronic localization functions, and the crystal orbitals. The contribution of atoms and polyhedra to birefringence was further evaluated using the Born effective charge. The results show that halogen atoms give negative contribution, and lead-oxygen polyhedra give positive contribution. The spin-orbit coupling effect is also investigated, and the downshift of the conduction band and variation in the valence band are found after relevant spin-orbit coupling (SOC), which leads to a reduction in the band gap and birefringence.

Structures, Electronic, and Magnetic Properties of CoKn (n = 2-12) Clusters: A Particle Swarm Optimization Prediction Jointed with First-Principles Investigation.

Transition-metal-doped clusters have long been attracting great attention due to their unique geometries and interesting physical and/or chemical properties. In this paper, the geometries of the lowest- and lower-energy CoKn (n = 2-12) clusters have been screened out using particle swarm optimization and first principles relaxation. The results show that except for CoK2 the other CoKn (n = 3-12) clusters are all three-dimensional structures, and CoK7 is the transition structure from which the lowest energy structures are cobalt atom-centered cage-like structures. The stability, the electronic structures, and the magnetic properties of CoKn clusters (n = 2-12) clusters are further investigated using the first principles method. The results show that the medium-sized clusters whose geometries are cage-like structures are more stable than smaller-sized clusters. The electronic configuration of CoKn clusters could be described as 1S1P1D according to the spherical jellium model. The main components of petal-shaped D molecular orbitals are Co-d and K-s states or Co-d and Co-s states, and the main components of sphere-like S molecular orbitals or spindle-like P molecular orbitals are K-s states or Co-s states. Co atoms give the main contribution to the total magnetic moments, and K atoms can either enhance or attenuate the total magnetic moments. CoKn (n = 5-8) clusters have relatively large magnetic moments, which has a relation to the strong Co-K bond and the large amount of charge transfer. CoK4 could be a magnetic superatom with a large magnetic moment of 5 µB.