Abstract Solar-driven CO2 reduction holds great promise for sustainable energy, yet the role of atomic active sites in governing intermediate formation and conversion remains poorly understood. Herein, a synergistic strategy using Ni single atoms (SAs) and surface oxygen vacancies (Ov) is reported to regulate the CO2 reduction pathway on the Bi2WO6 photocatalyst. Combining in-situ techniques and theoretical modeling, the reaction mechanism and the structure-activity relationship is elucidated. In-situ X-ray absorption spectroscopy identifies Bi and Ni as active sites, and in-situ diffuse reflectance infrared Fourier transform spectroscopy demonstrates that adsorption of H2O and CO2 readily forms CO32? species on the Ov-rich catalyst. Optimally balancing Ni SAs and Ov lowers the energy barrier for the formation and dehydration of a key COOH intermediate, leading to favorable CO formation and desorption. Consequently, a superior CO production efficiency of 53.49 µmol g?1 is achieved, surpassing previous reports on Bi2WO6-based catalysts for gas-phase CO2 photoreduction.

Since the past decade, enormous research efforts have been devoted to the detection/degradation and quantification of environmental toxic pollutants and biologically important molecules due to their ubiquitous necessity in the fields of environmental protection and human health. These fields of sensor and catalysis are advanced to a new era after emerging of nanomaterials, especially, carbon nanomaterials including graphene, carbon nanotube, carbon dots (C-dots), etc. Among them, the C-dots in the carbon family are rapidly boosted in the aspect of synthesis and application due to their superior properties of chemical and photostability, highly fluorescent with tunable, non/low-toxicity, and biocompatibility. The C-dot-based functional materials have shown great potential in sensor and catalysis fields for the detection/degradation of environmental pollutants. The major advantage of C-dots is that they can be easily prepared from numerous biomass/waste materials which are inexpensive and environment-friendly and are suitable for a developing trend of sustainable materials. This review is devoted to the recent development (since 2017) in the synthesis of biomass- and chemical-derived C-dots as well as diverse functionalization of C-dots. Their capability as a sensor and catalyst and respective mechanism are summarized. The future perspectives of C-dots are also discussed.

Recently, transition metal/metal oxides (TMMOs) decorated on porous carbons (PCs) have been intensively focused on designing rational electrode materials for the promising future specific category of electrochemical energy storage and conversion technologies. In particular, TMMO incorporation with PC structures has become very attractive in the area of supercapacitors (SCs) mainly caused by their large accessible surface areas (SSA), together with the suitable pore size distributions (PSD), high electrical conductivity, and rapid redox reactions reversibly on the surface. The transportation of ions, as well as electrons in the bulk of electrodes, is fast as a result of optimal contact between electrodes and electrolytes at the electrode-electrolyte interface, thereby generating high specific capacities (Csp) of these PCs with TMMOs. We report a survey regarding recent advances in the fabrication and synthesis of TMMOs decorated on PCs with some physical characteristics and their applications for electrochemical capacitors. Some future trends and prospects for further development of the subject nanocomposites in application to next-generation supercapacitors are discussed. © 2020 American Chemical Society.

In photodissociation of trans-formic acid (HCOOH) at 193 nm, we have observed two molecular channels of CO + H2O and CO2 + H2 by using 1 μs-resolved Fourier-transform infrared emission spectroscopy. With the aid of spectral simulation, the CO spectra are rotationally resolved for each vibrational state (v = 1–8). Each of the resulting vibrational and rotational population distributions is characteristic of two Boltzmann profiles with different temperatures, originating from either transition state pathway or OH-roaming to form the same CO + H2O products. The H2O roaming co-product is also spectrally simulated to understand the interplay with the CO product in the internal energy partitioning. Accordingly, this work has evaluated the internal energy disposal for the CO and H2O roaming products; especially the vibrational-state dependence of the roaming signature is reported for the first time. Further, given a 1 μs resolution, the temporal dependence of the CO/CO2 product ratio at v ≥ 1 rises from 3 to 10 of study, thereby characterizing the effect of conformational memory and well reconciling with the disputed results reported previously between absorption and emission methods. © 2020, The Author(s).

A new reaction scheme is proposed to account for roaming and chaotic behaviors in collisional and photo-initiated molecular-beam reactions, where nonadiabatic dynamics plays a key role and the collapse of superposition of wave functions is considered to be important in the beginning of the present scheme. Since the feature of molecular orbitals of reagents is crucial in reaction, we showed how to map out the spatial distribution of the relevant HOMO molecular orbitals of CH3Cl in the impact of fast electrons. We identified by experiment that the multiple overlap of nearby molecular orbitals affects even the vibrational motion of adjacent molecule DCl of the transient [ClDCl] chemical species. We also showed dynamical steric effects in the HBr + OH four-atom reaction as a manifestation of the nonadiabatic dynamics in complex systems. The roaming mechanism in the photo-initiated reaction of methyl formate is clarified in detail by experiment as well as the QCT trajectory calculation, where the conical intersection region plays an essential role. We suggest that two types of roaming trajectories coexist, i.e., deterministic and chaotic roaming trajectories based on classical trajectory calculations. To clarify the nonadiabatic dynamics in the roaming mechanism for non-collinear three-dimensional (3D) collisions, a new model of the 3D Polanyi rule is proposed as the extension of the well-established 2D Polanyi rule. In the 3D Polanyi rule, it is expected that the curvature and torsion of Frenet–Serret formulas in three-dimensional space would provide us key concepts in understanding reaction dynamics. © 2018, Accademia Nazionale dei Lincei.

An alternative to the transition state (TS) pathway, the roaming route, which bypasses the minimum energy path but produces the same molecular products, was recently found in photodissociation dynamics. This account describes signatures of roaming in photodissociation of the carbonyl compounds, specifically methyl formate and aliphatic aldehydes. Methyl formate was promoted to the excited state, followed by internal conversion via a conical intersection. Then, the energetic precursor dissociated to fragments which proceeded along either TS or roaming path. In contrast to the lack of a roaming saddle point found in methyl formate, the structure of the roaming saddle point for each of a series of aliphatic aldehydes comprises two moieties that are weakly bound at a distance. As its size increases, the energy difference between the TS barrier and the roaming saddle point increases and the roaming pathway becomes increasingly dominant. Experimentally, the rotational-level dependence of the roaming route was measured with ion imaging, while the vibrational-state dependence was observed with time-resolved Fourier-transform infrared emission spectroscopy. The roaming signature was verified theoretically by quasi-classical trajectory (QCT) calculations. As an alternative to the QCT method, a multi-center impulsive model was developed to simulate the roaming scalar and vector properties. © 2018 Informa UK Limited, trading as Taylor & Francis Group.

This paper proposes a new type of roaming mechanism. We find a signature of trajectory with chaotic behavior in the action-angle diagram of the H + H2 reaction on a LEP surface, namely the trajectory is found to be very sensitive to the initial angle variable which corresponds to the phase of the H2 vibration. The trajectory pattern switches from the direct to the complex forming mechanism, and vice versa, in the angle range (0 ∼ π). In the complex forming angle range, trajectories switch from reactive to non-reactive randomly and suddenly, as the result, we cannot predict the collision pattern from the initial conditions. Therefore, we may classify such trajectory as a new type of roaming with chaotic behavior, and it is different from the ordinary trajectory with deterministic behavior. This chaotic behavior could be due cooperative nearby network interaction (CNN effect). We also suggest that the KPP (Kolmogorow-Petrovsky-Piskounov) equation is useful to estimate the density gradient of the activated reagents, so that one can evaluate the branching ratio to various exit channels, such as triple fragmentation, tight transition state, or the roaming channel with the aid of the present classical trajectory calculation. © 2017 Author(s).

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Carbonyl compounds studied are confined to acetyl halide (CH3COCl), acetyl cyanide (CH3COCN), acetyl sulfide (CH3COSH), acetaldehyde (CH3CHO), and methyl formate (HCOOCH3). They are asymmetrically substituted, but do not follow the well-known Norrish type I reactions. Each compound ejected in an effusive beam at about 300 K is commonly excited to the 1(n, π∗)CO lower state; that is, a nonbonding electron on O of the C=O group is promoted to the antibonding orbital of π∗CO. The photolysis experiments are conducted in the presence of Ar gas and the corresponding fragments are detected using time-resolved Fourier-transform Infrared (FTIR) emission spectroscopy. The enhancement of the collision-induced internal conversion or intersystem crossing facilitates the dissociation channels via highly vibrational states of the ground singlet (So) or triplet (T1) potential energy surfaces. In this manner, an alternative nonadiabatic channel is likely to open yielding different products, even if the diabatic coupling strength is strong between the excited state and the neighboring state. For instance, the photodissociation of CH3COCl at 248 nm produces HCl, CO, and CH2 fragments, in contrast to the supersonic jet experiments showing dominance of the Cl fragment eliminated from the excited state. If the diabatic coupling strength is weak, dissociation proceeds mainly through internal conversion, such as the cases of CH3COCN and CH3COSH. The photodissociation of CH3COCN at 308 nm has never been reported before, while for CH3COSH matrix-isolated photodissociation was conducted that shows a distinct spectral feature from the current FTIR method. The CH3CHO and HCOOCH3 molecules belong to the same type of carbonyl compounds, in which the molecular products, CO + CH4 and CO + CH3OH, are produced through both transition state and roaming pathways. Their products are characterized differently between molecular beam and current FTIR experiments. For instance, the photodissociation of HCOOCH3 at 248 nm yields CO with the vibrational state v ≥ 4, in contrast to the molecular beam experiments producing CO at v = 1. The photodissociation of CH3CHO at 308 nm intensifies a low energy component in the CH4 vibrational distribution, thus verifying the transition state pathway for the first time. © the Owner Societies 2016.

Electrostatic hexapoles are revealed as a powerful tool in the rotational state-selection and alignment of molecules to be utilized in beam experiments on collisional and photoinitiated processes. In the paper, we report results on the application of the hexapolar technique on the recently studied chiral molecules propylene oxide, 2-butanol and 2-bromobutane, to be investigated in selective photodissociation and enantiomeric discrimination. © 2016 Author(s).

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Photodissociation of isobutyraldehyde (C3H7CHO) at 248 nm is investigated using time-resolved Fourier-transform infrared emission spectroscopy to demonstrate the growing importance of the roaming pathway with increasing molecular size of aliphatic aldehydes. Each acquired CO rotational distribution from v = 1 to 4 is well characterized by a single Boltzmann rotational temperature from 637 to 750 K, corresponding to an average rotational energy of 5.9 ± 0.6 kJ mol-1. The roaming signature that shows a small fraction of CO rotational energy disposal accompanied by a vibrationally hot C3H8 co-fragment is supported by theoretical prediction. The energy difference between the tight transition state (TS) and the roaming saddle point (SP) is found to be -27, 4, 15, 22, and 30 kJ mol-1 for formaldehyde, acetaldehyde, propionaldehyde, isobutyraldehyde, and 2,2-dimethyl propanal, respectively. The roaming SP is stabilized by a larger alkyl moiety. It is suggested that the roaming photodissociation rate of aldehydes increasingly exceeds those via the tight TS, resulting in the dominance of the CO + alkane products, as the size of aldehydes becomes larger. Along with formaldehyde, acetaldehyde, and propionaldehyde, in this work isobutyraldehyde is further demonstrated that this aldehyde family with special functional group is the first case in the organic compound to follow predominantly a roaming dissociation pathway, as the molecular size becomes larger. © the Owner Societies 2015.

The exploration of alternative roads that open to molecules with sufficient energy to yield different products permits prediction and eventually control of the outcomes of chemical reactions. Advanced imaging techniques for monitoring laser-induced photodissociation are here combined with dynamical simulations, involving ample sets of classical trajectories generated on a quantum chemical potential energy surface. Methyl formate, HCOOCH3, is photodissociated at energies near the triple fragmentation threshold into H, CO and OCH3. Images of velocity and rotational distributions of CO exhibit signatures of alternative routes, such as those recently designated as transition-state vs. roaming-mediated. Furthermore, a demonstration of the triple fragmentation route is given, and also confirmed by H-atom product imaging and FTIR time-resolved spectra of the intermediate HCO radical. In addition, the relevance of nonadiabatic transitions promoted by a conical intersection is clarified by simulations as the privileged "reactivity funnel" of organic photochemistry, whereby the outcomes of molecular photoexcitation are delivered to electronic ground states. This journal is © the Owner Societies 2014.

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