Multiscale Simulation of Morphology Evolution of Supported Pt Nanoparticles via Interfacial Control.

The structural and electronic properties of the interface are critical for the morphology of supported metal nanoparticles and thus the performance in catalysis, photonics, biomedical research, and other areas. To reveal the intrinsic mechanism of the formation of various morphologies, a multiscale simulation strategy is adopted to bridge the macroscopic structures by experimental observations and microscopic properties by theoretical calculations. This strategy incorporates the density functional theory (DFT) for the interaction energy calculation, the molecular dynamics (MD) simulation for the structure evolution, and theoretical model for the correlation with contact angles. The interaction energies between Pt atoms (four-atom clusters) and substrates are applied for the force field parametrization in the following MD simulation. Simulation results show the binding energies and structural properties such as radial distribution function and coordination number for supported metal nanoparticles with various sizes in detail. Notably, the contact angles of supported nanoparticles are well correlated by the strength of metal-support interactions. This work yields guidelines on the structure modulation of supported metal nanoparticles via interfacial control.

Single and double boron atoms doped nanoporous C2N-h2D electrocatalysts for highly efficient N2 reduction reaction: a density functional theory study.

The electrocatalytical process is the most efficient way to produce ammonia (NH3) under ambient conditions, but developing a highly efficient and low-cost metal-free electrocatalysts remains a major scientific challenge. Hence, single atom and double boron (B) atoms doped 2D graphene-like carbon nitride (C2N-h2D) electrocatalysts have been designed (B@C2N and B2@C2N), and the efficiency of N2 reduction reaction (NRR) is examined by density functional theory calculation. The results show that the single and double B atoms can both be strongly embedded in natural nanoporous C2N with superior catalytic activity for N2 activation. The reaction mechanisms of NRR on the B@C2N and B2@C2N are both following an enzymatic pathway, and B2@C2N is a more efficient electrocatalyst with extremely low overpotential of 0.19 eV comparing to B@C2N (0.29 eV). In the low energy region, the hydrogenation of N2 is thermodynamically more favorable than the hydrogen production, thereby improving the selectivity for NRR. Based on these results, a new double-atom strategy may help guiding the experimental synthesis of highly efficient NRR electrocatalysts.

Micromechanical simulation of the pore size effect on the structural stability of brittle porous materials with bicontinuous morphology.

Brittle porous materials offer a wide variety of promising applications due to their high surface-area-to-volume ratios and controllable porous structures. Getting comprehensive knowledge of the structural stability is of great significance for avoiding the irreversible destruction of these materials. Based on interpenetrating bicontinuous structures, we innovatively adopted a sequential mesoscopic simulation strategy to show the pore size effect on the mechanical stability, which involves structural evolution by the mesoscale dynamic density functional method and mechanical behavior by the highly efficient lattice spring model. Simulation results show that specific surface areas, Young's moduli and fracture strains decrease with the increase of pore widths on the premise of the same porosity. More uniform stress/strain distributions are observed in structures with smaller pore sizes or more uniform defect distributions. From the local stress distribution analysis, the effective stress transfer occurs in the solid phase, which runs through the simulation box along the tensile direction, and the mechanical disparity among systems with different pore sizes is due to different volume fractions and microstructures of the solid phase. Larger pore sizes result in lower Weibull moduli due to the increased heterogeneity and a less predictable failure behavior, and the concentrated defects usually result in mechanical anisotropy.

In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution.

Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis. Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt-cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co(0), CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method. CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER. Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nanoparticles, and the introduction of electron-rich nitrogen. In addition, when used as catalysts of OER, the CoOx@CN hybrids required 0.26 V overpotential for a current density of 10 mA cm(-2), which is comparable even superior to many other non-noble metal catalysts. More importantly, an alkaline electrolyzer that approached ∼20 mA cm(-2) at a voltage of 1.55 V was fabricated by applying CoOx@CN as cathode and anode electrocatalyst, which opened new possibilities for exploring overall water splitting catalysts.

Tripodal Pd metallenes mediated by Nb2C MXenes for boosting alkynes semihydrogenation.

2D metallene nanomaterials have spurred considerable attention in heterogeneous catalysis by virtue of sufficient unsaturated metal atoms, high specific surface area and surface strain. Nevertheless, the strong metallic bonding in nanoparticles aggravates the difficulty in the controllable regulation of the geometry of metallenes. Here we propose an efficient galvanic replacement strategy to construct Pd metallenes loaded on Nb2C MXenes at room temperature, which is triggered by strong metal-support interaction based on MD simulations. The Pd metallenes feature a chair structure of six-membered ring with the coordination number of Pd as low as 3. Coverage-dependent kinetic analysis based on first-principles calculations reveals that the tripodal Pd metallenes promote the diffusion of alkene and inhibit its overhydrogenation. As a consequence, Pd/Nb2C delivers an outstanding turnover frequency of 10372 h-1 and a high selectivity of 96% at 25 oC in the semihydrogenation of alkynes without compromising the stability. This strategy is general and scalable considering the plentiful members of the MXene family, which can set a foundation for the design of novel supported-metallene catalysts for demanding transformations.

Effects of manganese on the catalytic performance of CuCo catalysts for direct conversion of CO/CO2 to higher alcohols.

The catalytic conversion of CO or CO/CO2 mixtures to higher alcohols (HAs) using hydrogenation reactions remains challenging in C1 chemistry and also one of the most promising reactions for the utilization of non-petroleum resources. Here, the experiment and characterization tests of CuCoMn/Al2O3 show that copper is much more dispersed on γ-Al2O3 than cobalt, and the interaction between cobalt and Mn metals is stronger. And, mixed cobalt-manganese oxides are formed in the calcined catalyst, promoting the formation of higher alcohols. Under the optimum conditions, the catalyst demonstrated a total alcohol selectivity of 44.6%, and the fraction of higher alcohols reached up to 85.3% among the total alcohol products, which is superior to the classical modified CuCo-based catalysts. And in the gas mixture reaction with a CO : CO2 ratio of 8 : 2, the conversion rate of the catalyst to CO and CO2 reached 34.8% and 27.3%, respectively, and the selectivity (C1+ slate 1-alcohol) was 53.2%.

Ru Supported on p-phthalic acid-Mn Derived from a Mn Metal-Organic Framework for Thermo- and Electrocatalytic Synthesis of Ethylene-D4 Glycol.

Deuterium-labeled polyols are one of the most extensive applied chemicals in biochemistry and biophysics. However, the deuteriation still is insufficient, exhibiting a low deuterated ratio and indistinct reaction mechanism. Herein, Ru supported on MnBCD (MnBDC, derived from Mn p-phthalic acid metal-organic framework) as nanocatalyst with an agglomerated sheet-type structure; this allows the possibility of achieving both thermo- and electrocatalytic hydrogen isotope exchange (HIE) reaction. Furthermore, XPS characterization confirmed that the specific structural changes in the electron density of Ru outer layers were modulated through the impregnation and reduction processes. According to the change of outer electronic structure, hydrogen spillover and electron-rich flow promote the reaction of the catalyst in thermo- and electrocatalytic systems, respectively. In addition, the results indicate that a high deuterated ratio of 97 % can be obtained, hence the catalytic technology has enormous potential for the synthesis of a broad variety of deuterium-labeled compounds.

Heteroatom-Doping of Non-Noble Metal-Based Catalysts for Electrocatalytic Hydrogen Evolution: An Electronic Structure Tuning Strategy.

Electrocatalytic water splitting for hydrogen production is an appealing way to reduce carbon emissions and generate renewable fuels. This promising process, however, is limited by its sluggish reaction kinetics and high-cost catalysts. Construction of low-cost and high-performance non-noble metal-based catalysts have been one of the most effective approaches to address these grand challenges. Notably, the electronic structure tuning strategy, which could subtly tailor the electronic states, band structures, and adsorption ability of the catalysts, has become a pivotal way to further enhance the electrochemical water splitting reactions based on non-noble metal-based catalysts. Particularly, heteroatom-doping plays an effective role in regulating the electronic structure and optimizing the intrinsic activity of the catalysts. Nevertheless, the reaction kinetics, and in particular, the functional mechanisms of the hetero-dopants in catalysts yet remains ambiguous. Herein, the recent progress is comprehensively reviewed in heteroatom doped non-noble metal-based electrocatalysts for hydrogen evolution reaction, particularly focus on the electronic tuning effect of hetero-dopants in the catalysts and the corresponding synthetic pathway, catalytic performance, and activity origin. This review also attempts to establish an intrinsic correlation between the localized electronic structures and the catalytic properties, so as to provide a good reference for developing advanced low-cost catalysts.

Thermal Puffing Promoting the Synthesis of N-Doped Hierarchical Porous Carbon-CoO x Composites for Alkaline Water Reduction.

N-doped porous carbon-based catalysts hold great promise for hydrogen evolution reaction (HER) due to their plentiful cavity construction, high specific surface area, and flexible metal assemblies. Nevertheless, the cumbersome synthetic process and the use of highly corrosive chemicals greatly increase the production costs and pollutions. Herein, we report a facile and eco-friendly thermal puffing strategy, which imitates the popcorn forming process, for the fabrication of N-doped hierarchical porous carbon-CoO x catalysts. The results indicate that the well-developed porosity and high specific surface area (696 m2 g-1) of CoO x -NC-1.0 are achieved during the thermal expansion. Impressively, the as-prepared CoO x -NC-1.0 with ultralow Co loading (0.67 wt %) presents admirable HER performance to drive 10 mA cm-2 at an overpotential of 189 mV in the alkaline electrolyte. Especially, the activity of CoO x -NC-1.0 can be maintained for a continuous ∼70 h test. Such an excellent property of CoO x -NC not only derives from the hierarchical porous structure but is also due to the higher ratio of graphitic-N and pyridinic-N, which promotes the better electrical conductivity and formation of more active Co0 for HER, respectively. Moreover, this strategy is applicable to the fabrication of other transition metal-based hierarchical porous composites, which opens new possibilities for exploring promising candidates to substituted commercial Pt/C.

Multiscale Simulation on Product Distribution from Pyrolysis of Styrene-Butadiene Rubber.

Pyrolysis of styrene-butadiene rubber receives renewed attention due to its application in tackling the waste tire disposal problem while allowing energy recovery. The density functional theory calculation (DFT) and ReaxFF molecular dynamics simulation (MD) are adopted to study the pyrolysis process with the variation of temperature and pressure. The bond dissociation energies of intramonomer and intermonomer bonds in trimers with different linking methods are calculated by DFT, where the bond with low energy tends to break during the pyrolysis process. The following MD simulation shows the pyrolysis product distribution of chain segments in styrene-butadiene rubber, where bond breaking positions in MD agree well with corresponding results in DFT and experiment. The next nearest neighbor bonds (single bonds) connected with double bond or benzene usually have lower dissociation energies than other single bonds and prone to break during the pyrolysis process. And thus, the intermonomer bonds tend to break at relatively low temperatures (around 650 K in experiment) prior to intramonomer bonds, which result in the emergence of monomers. With the temperature increase, intramonomer bonds are broken and thus large fragments are further pyrolyzed into small ones (e.g., C2 and C). Besides, the pressure strongly influences the product distribution, where high pressures promote the occurrence of secondary reactions.

Dominating Role of Ni0 on the Interface of Ni/NiO for Enhanced Hydrogen Evolution Reaction.

The research of a robust catalytic system based on single NiOx electrocatalyst for hydrogen evolution reaction (HER) remains a huge challenge. Particularly, the factors that dominate the catalytic properties of NiOx-based hybrids for HER have not been clearly demonstrated. Herein, a convenient protocol for the fabrication of NiOx@bamboo-like carbon nanotube hybrids (NiOx@BCNTs) is designed. The hybrids exhibit superb catalytic ability and considerable durability in alkaline solution. A benchmark HER current density of 10 mA cm-2 has been achieved at an overpotential of ∼79 mV. In combination with the experimental results and density functional theory (DFT) calculations, this for the first time definitely validates that the inherent high Ni0 ratio and the Ni0 on the interface of Ni/NiO play a vital role in the outstanding catalytic performance. Especially, the Ni0 on the interface of Ni/NiO performs superior activity for water splitting compared with that of bulk Ni0. These conclusions provide guidance for the rational design of the future non-noble metallic catalysts.

Ni-promoted synthesis of graphitic carbon nanotubes from in situ produced graphitic carbon for dehydrogenation of ethylbenzene.

Graphitic carbon nanotubes (GCNTs) were fabricated from in situ produced graphitic carbon by calcining biomass/melamine/Ni(NO3)2·6H2O. Ni-based hybrids (NiOx@GCNTs) displayed superior catalytic capacity in direct dehydrogenation of ethylbenzene. The specific reaction rate can reach up to 8.1 µmol m(-2) h(-1), and unprecedented stability was obtained over 165 h without any activation process.

Updating biomass into functional carbon material in ionothermal manner.

The development of meaningful ways to transfer biomass into useful materials, more efficient energy carriers, and/or carbon storage deposits is a profound challenge of our days. Herein, an ionothermal carbonization (ITC) method, via treating natural resources (glucose, cellulose, and sugar cane bagesse) in nonmetal ionic liquids (ILs) at ∼200 °C, is established for the fabrication of porous heteroatom-doped carbon materials with high yield. Commercial ILs with bulky bis(trifluoromethylsulfonyl)imide anion or cross-linkable nitrile group were found to be efficient and recyclable templates for porosity control, leading to exciting nanoarchitectures with promising performance in oxygen reduction reaction. The optimized ILs (12 mL) can dissolve and directly convert up to 15 g of glucose into porous carbon materials (SBET: 272 m(2)/g) one time. This ITC method relies on the synergistic use of structure-directing effect, good biomass solubility, and excellent thermal stability of ILs, and provides a sustainable strategy for exploiting biomass.

Design and fabrication of hierarchically porous carbon with a template-free method.

Fabrication of hierarchically porous carbon materials (HPCs) with high surface area and pore volume has always been pursued. However, the currently effective template methods and acid/base activation strategies suffer from the drawbacks of either high costs or tedious steps. Herein, HPCs with 3D macro-mesopores and short-range meso-micropores were fabricated via an easy and sustainable two-step method from biomass. Macro-mesopores were constructed by slightly accumulation/aggregation of carbon spheres ranging from 60 nm to 80 nm, providing efficient mass diffusion pathways. Short-range mesopores and micropores with high electrolyte accessibility were developed in these spheres by air activation. The obtained HPCs showed surface area values up to 1306 m(2)/g and high mesopore volume proportion (63.9%). They demonstrated excellent capacitance and low equivalent series resistance (ESR) as supercapacitor electrode materials, suggesting the efficient diffusion and adsorption of electrolyte ions in the designed hierarchically porous structure.

Combination of carbon nitride and carbon nanotubes: synergistic catalysts for energy conversion.

Due to their versatile features and environmental friendliness, functionalized carbon materials show great potential in practical applications, especially in energy conversion. Developing carbon composites with properties that can be modulated by simply changing the ratio of the original materials is an intriguing synthetic strategy. Here, we took cyanamide and multiwalled carbon nanotubes as precursors and introduced a facile method to fabricate a series of graphitic carbon nitride/carbon nanotubes (g-C3 N4 /CNTs) composites. These composites demonstrated different practical applications with different weight ratios of the components, that is, they showed synergistic effects in optoelectronic conversion when g-C3 N4 was the main ingredient and in oxygen reduction reaction (ORR) when CNTs dominated the composites. Our experiments indicated that the high electrical conductivity of carbon nanotubes promoted the transmission of the charges in both cases.