Controlled evolution of surface microstructure and phase boundary of ZnO nanoparticles for the multiple sensitization effects on triethylamine detection.

In ZnO gas sensors, donor defects (such as zinc interstitials and oxygen vacancies) are considered active sites for the chemical adsorption and ionization of oxygen on the surface of ZnO, which can significantly enhance the sensor's response. However, the influence of the surface microstructure and phase boundaries of ZnO nanoparticles on the chemical adsorption and ionization of surface oxygen has rarely been explored. In this study, we developed a mixed-phase ZnO nanoparticle gas sensor with a rich phase boundary showing 198-50 ppm improvement in response to triethylamine at 340 °C. This is attributed to the generation of defects originating from lattice mismatch at the ZnO - zincite phase boundaries, which providing more active sites for adsorption of oxygen and triethylamine molecules. This work demonstrates a feasible method of combining surface microstructure regulation with pyrolysis strategies to develop ZnO sensors with significantly enhanced gas response performance.

Fabrication of a Molybdenum Dioxide/Multi-Walled Carbon Nanotubes Nanocomposite as an Anodic Modification Material for High-Performance Microbial Fuel Cells.

A nanocomposite of multi-walled carbon nanotubes (MWCNTs) decorated with molybdenum dioxide (MoO2) nanoparticles is fabricated through the reduction of phosphomolybdic acid hydrate on functionalized MWCNTs in a hydrogen-argon (10%) atmosphere in a tube furnace. The MoO2/MWCNTs composite is proposed as an anodic modification material for microbial fuel cells (MFCs). MWCNTs have outstanding physical and chemical peculiarities, with functionalized MWCNTs having substantially large electroactive areas. In addition, combined with the exceptional properties of MoO2 nanoparticles, the synergistic advantages of functionalized MWCNTs and MoO2 nanoparticles give a MoO2/MWCNTs anode a large electroactive area, excellent electronic conductivity, enhanced extracellular electron transfer capacity, and improved nutrient transfer capability. Finally, the power harvesting of an MFC with the MoO2/MWCNTs anode is improved, with the MFC showing long-term repeatability of voltage and current density outputs. This exploratory research advances the fundamental application of anodic modification to MFCs, simultaneously providing valuable guidance for the use of carbon-based transition metal oxide nanomaterials in high-performance MFCs.

First-principle calculations study of the ORR/OER electrocatalytic activity of ruthenium polyphthalocyanine axially modified with aliphatic thiol groups.

In this study, the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalytic activity of ruthenium polyphthalocyanine axially modified with different aliphatic thiol groups, RuPPc-SR (SR = -SCH3, -SC2H5, -SC3H7, -SC4H9, -SC5H11, and -SC6H13), in an acidic medium were simulated using DFT. All -SR groups can effectively enhance the ORR and OER catalytic activities of RuPPc. The ORR and OER overpotentials of RuPPc-SC4H9 are 0.237 V and 0.436 V, respectively, which are far lower than those of RuPPc (0.960 V and 0.903 V). For RuPPc-SC4H9, the four C and S atoms of the -SC4H9 chain and Ru atom are coplanar, and thus, conjugate effects and inductive effects exist between the -SC4H9 chain and Ru atom. This makes the Ru atom exhibit the least positive Bader charge and smallest spin density, and the anti-bonding orbitals of dxz, dyz, and dz2 of the Ru atom shift below the Fermi level (Ef). This makes the adsorption strength of RuPPc-SC4H9 toward ORR and OER intermediates the weakest, which accelerates the reaction process, thus resulting in better ORR and OER catalytic activity. Therefore, the introduction of the aliphatic thiol groups might effectively improve the OER/ORR catalytic activity of RuPPc.

Cu@CuOx/WO3 with photo-regulated singlet oxygen and oxygen adatoms generation for selective photocatalytic aromatic amines to imines.

Photocatalysts can absorb light and activate molecular O2 under mild conditions, but the generation of unsuitable reactive oxygen species often limits their use in synthesizing fine chemicals. To address this issue, we disperse 1 wt% copper on tungsten trioxide (WO3) support to create an efficient catalyst for selective oxidative coupling of aromatic amines to imines under sunlight irradiation at room temperature. Copper consists of a metallic copper core and an oxide shell. Experimental and density functional theory calculations have confirmed that Cu2O is the primary activation site. Under λ < 475 nm, the light excites electrons of the valence bands in Cu2O and WO3, which activate O2 to superoxide radical •O2-. Then rapidly transforms into oxygen adatoms (•O) and oxygen anion radicals (•O-) species on the surface of Cu2O. Simultaneously, it is captured by holes in the WO3 valence band to generate singlet oxygen (1O2). •O bind to 1O2 promoting the coupling reaction of amines. When λ > 475 nm, intense light absorption due to the localized surface plasmon resonance excites numerous electrons in Cu to promote the oxidative coupling with the adsorbed O2. This study presents a promising approach towards the design of high-performance photocatalysts for solar energy conversion and environmentally-friendly oxidative organic synthesis.

Galvanic replacement-induced preparation of bloom-like Pt23Ni77 for methanol coupled efficient hydrogen production.

Galvanic replacement reaction (GRR) leverages the difference in metal reduction potentials to regulate the structure of nanomaterials. The crucial aspect of constructing highly active catalysts lies in the precise manipulation of both the oxidative dissolution of sacrificial template metals and reductive deposition of alternate metals. Herein, we investigated the morphological transformation of metal Ni as a sacrificial template in the presence of different amounts of H2PtCl6 solution and the Pt4+ substitution of Ni to achieve the redistribution of elements on the catalyst surface, which provides superior performance in both the methanol oxidation reaction (MOR) and hydrogen evolution reaction (HER). The uniform distribution of Pt on a three-dimensional transition metal Ni substrate allows for the complete exposure of the noble metal to the catalyst surface. This distribution increases the reaction area, facilitating easy access for reactants and promoting electron transfer. Meanwhile, Pt (1.39 Å) has a larger atomic radius compared to Ni (1.24 Å), and the substitution reaction in the transition metal phase induces strong compressive strain, which effectively regulates the electronic structure of Ni.

Facile electrolysis-solvothermal synthesis of NiOx/graphene for enhanced ethanol oxidation to acetate.

In this work, low-crystalized and defective NiOx/graphene was synthesized by a facile electrolysis-solvothermal method. In the electrolytic process, Ni ions originate from the Ni anode, and graphene is produced from the graphite cathode. Then, Ni ions are reduced into oxides and deposited on graphene in the subsequent solvothermal process. The NiOx/graphene displays excellent electrocatalytic activity and selectivity for ethanol oxidation reaction to acetate. The peak current density was 296.5 mA cm-2 on a glassy carbon electrode. The FE of acetate was more than 93% at the potential range between 1.4 and 1.7 V. We propose that the mechanism is a cooperation between the chemical deprotonating process of ethanol by Ni3+ species and the electrochemical oxidation of the CH3CH2O* intermediate to acetate at the interface between NiOx and graphene.

Structural and Chemical Bonding Properties of AuS2H0/-: A Photoelectron Velocity-Map Imaging Spectroscopic and Theoretical Study.

Mass-selected photoelectron velocity-map imaging spectroscopy was employed to investigate the geometrical and electronic properties of AuS2H-/0. The comprehensive comparison between the experiment and theoretical calculations establishes that the ground-state AuS2H- anion has a mixed-ligand structure [SAuSH]- with an unsymmetrical S-Au-S unit. Further chemical bonding analyses on AuS2H and comparison with the isoelectronic AuS2- suggest that the unique S-Au-S unit in these species features two three-center, three-electron π-bonding, and one three-center, two-electron σ-bonding. The isoelectronic replacement of the extra electron in AuS2- by the H atom can lead to σ bonding evolution from the electron-sharing bond to the dative bond. These findings are conducive to the fundamental understanding of the intrinsic stability of thiolate-protected gold nanoclusters and their delicate ligand design to achieve desirable properties.

A Universal Approach for Sustainable Urea Synthesis via Intermediate Assembly at the Electrode/Electrolyte Interface.

Electrocatalytic C-N coupling process is indeed a sustainable alternative for direct urea synthesis and co-upgrading of carbon dioxide and nitrate wastes. However, the main challenge lies in the unactivated C-N coupling process. Here, we proposed a strategy of intermediate assembly with alkali metal cations to activate C-N coupling at the electrode/electrolyte interface. Urea synthesis activity follows the trend of Li+

Fe-induced crystalline-amorphous interface engineering of a NiMo-based heterostructure for enhanced water oxidation.

Engineering heterostructures with a unique surface/interface structure is one of the effective strategies to develop highly active noble-metal-free catalysts for the oxygen evolution reaction (OER), because the surface/interface of catalysts is the main site for the OER. Herein, we design a coralloid NiMo(Fe)-20 catalyst with a crystalline-amorphous interface through combining a hydrothermal method and an Fe-induced surface reconfiguration strategy. That is, after Fe3+ impregnation treatment, the Ni(OH)2-NiMoO4 pre-catalyst with a complete crystalline surface is restructured into a trimetallic heterostructure with a crystalline-amorphous interface, which facilitates mass diffusion and charge transfer during the OER. As expected, self-supported NiMo(Fe)-20 exhibits excellent electrocatalytic water oxidation performance (overpotential: η-10 = 220 mV, η-100 = 239 mV) in the alkaline electrolyte, and its electrocatalytic performance hardly changes after maintaining the current density of 50 mA cm-2 for 10 hours. Furthermore, nickel foam (NF) supported commercial Pt/C and self-supported NiMo(Fe)-20 served as the cathode and anode of the Pt/C‖NiMo(Fe)-20 electrolyzer, respectively, which exhibits a lower cell voltage (E-100 = 1.53 V) than that of the Pt/C‖RuO2 electrolyzer (E-100 = 1.58 V) assembled with noble metal-based catalysts. The enhanced electrocatalytic performance of the NiMo(Fe)-20 catalyst is mainly attributed to the synergistic effect between the crystalline-amorphous interface and the coralloid trimetallic heterostructure.

Interfacial carbon dots introduced distribution-structure modulation of Pt loading on graphene towards enhanced electrocatalytic hydrogen evolution reaction.

To easily load Pt on smoothy graphene synthesized by cathodic exfoliation method and achieve adjacent plane distribution of Pt, carbon dots (CDs) are used to construct anchoring points to load highly dispersed Pt species due to strong interaction between CDs and Pt species. The composite of Pt-CDs/graphene is synthesized via a continuous process of cathodic exfoliation-hydrothermal-impregnation-reduction. Characterization results indicate the distribution configuration of Pt varies from coated structure of CDs@Pt to dispersed configuration of CDs&Pt or Pt&CDs, then to wrapping configuration of Pt@CDs with increased amount of CDs. It's found that suitable introduction of CDs promotes the adjacent plane distribution of Pt species. The obtained best Pt-4CDs/G shows the low overpotential of 36 mV (10 mA⋅cm-2) and high mass activity of 3747.8 mA mg-1 at -40 mV towards electrocatalytic hydrogen evolution reaction (HER), 9.2 times more active than that of Pt/C (406.2 mA mg-1). The superior HER performance of Pt-4CDs/G is attributed to its relatively adjacent plane distribution of Pt, which supports high electrochemically active surface area and more adjacent Pt sites for H* adsorption. Benefitting from that, the HER process for Pt-4CDs/G favorably follows the Tafel pathway, resulting in low hydrogen adsorption free energy and excellent HER activity.

Controlled Growth of Pd Nanocrystals by Interface Interaction on Monolayer MoS2: An Atom-Resolved in Situ Study.

The crystal growth kinetics is crucial for the controllable preparation and performance modulation of metal nanocrystals (NCs). However, the study of growth mechanisms is significantly limited by characterization techniques, and it is still challenging to in situ capture the growth process. Real-time and real-space imaging techniques at the atomic scale can promote the understanding of microdynamics for NC growth. Herein, the growth of Pd NCs on monolayer MoS2 under different atmospheres was in situ studied by environmental transmission electron microscopy. Introducing carbon monoxide can modulate the diffusion of Pd monomers, resulting in the epitaxial growth of Pd NCs with a uniform orientation. The electron energy loss spectroscopy and theoretical calculations showed that the CO adsorption assured the specific exposed facets and good uniformity of Pd NCs. The insight into the gas-solid interface interaction and the microscopic growth mechanism of NCs may shed light on the precise synthesis of NCs on two-dimensional (2D) materials.

A theoretical study on the ORR electrocatalytic activity of axial ligand modified cobalt polyphthalocyanine.

In this work, the catalytic activity in the oxygen reduction reaction (ORR) of cobalt polyphthalocyanine whose central Co atom is coordinated at the axial position by ligands (L = -F, -OH, -OCH3, -N3, -Cl, -Br, -I, -SCN, and -CN) (CoPPc-L) was investigated using theoretical calculations in alkaline medium. Among all CoPPc-L, CoPPc-N3 exhibited the lowest ORR overpotential of 0.23 V vs. a standard hydrogen electrode, which is significantly lower than those of CoPPc (0.48 V) and Pt(111) (0.43 V). There is a good linear relationship between ΔG*OOH and the electronegativity of ligating atoms in axial ligands of CoPPc-L. The greater the electronegativity, the stronger the adsorption of the catalyst to the intermediate. Additionally, the adsorption strength of CoPPc to the intermediate is modified by the axial ligands, which adjust the distribution of anti-bonding electronic states of dz2, dxz, and dyz orbitals near the Fermi level, Ef. A larger Mayer bond order of the Co-L bond resulted in a smaller bond order of the Co-O bond. CoPPc-N3 exhibited a moderate Co-O bond order of 0.737, corresponding to moderate adsorption energy to the OOH intermediate. This study demonstrates that the interaction strength between CoPPc and ORR intermediates can be adjusted by selecting appropriate axial ligands, which can modulate the ORR catalytic activity.

Strain-tunable magnetism and topological states in layered VBi2Te4.

Similar to the magnetic topological insulator of MnBi2Te4, recent studies have demonstrated that VBi2Te4 is also an ideal candidate to explore many intriguing quantum states. Different from the strong interlayer antiferromagnetic (AFM) coupling in layered MnBi2Te4, based on first-principles calculations, we find that the energy difference between AFM and ferromagnetic (FM) orders in layered VBi2Te4 is much smaller than that of MnBi2Te4. Specifically, it is found that the interlayer FM coupling can be readily achieved by applying strain. Further electronic band structures reveal that the VBi2Te4 bilayer is a time-reversal symmetry broken quantum spin Hall insulator with a spin Chern number of CS = 1, which is essentially different from the QAH state with a Chern number of C = 1 in the MnBi2Te4 bilayer. Most strikingly, the topological states of the magnetic VBi2Te4 bilayer can be well tuned by strain, whose topological phase diagram is mapped out as a function of strain by employing continuum model analyses. All of these results indicate that the layered VBi2Te4 not only enriches the family of magnetic topological materials, but also provides a promising platform to explore more exotic quantum phenomena.

Bi2Te3-intercalated MnBi2Te4: ideal candidate to explore intrinsic Chern insulator and high-temperature quantum anomalous Hall effect.

The recently discovered magnetic topological insulator of MnBi2Te4(MBT), has been demonstrated to realize the quantum anomalous Hall (QAH) effect, while the naturally antiferromagnetic (AFM) interlayer coupling in MBT results in that the QAH effect can only be realized in odd-layered systems and at low temperature. Using first-principles calculations, we find that intercalating Bi2Te3(BT) layers into MBT by forming MBT/(BT)n/MBT (n= 1-6) heterostructures can induce magnetic phase transition from AFM to ferromagnetic (FM) interlayer coupling whenn⩾ 3. Specifically, MBT/(BT)3/MBT and MBT/(BT)4/MBT respectively host Curie temperaturesTcof 14 K and 11 K, which fits well the experimentally measuredTcof 12 K. Detailed band structure calculations and topological identification show that the QAH phases are well preserved for all FM heterostructures. And the topological mechanism of MBT/(BT)n/MBT as a function ofnis revealed by employing continuum model analysis. Most importantly, the FM MBT/(BT)4/MBT has already been experimentally fabricated. Thus, our work provides a practical guideline to explore high-temperature QAH effect in MBT family of materials.

Engineering topological states in a two-dimensional honeycomb lattice.

In this work, we use first-principles calculations to determine the interplay between spin-orbit coupling (SOC) and magnetism which can not only generate a quantum anomalous Hall state but can also result in topologically trivial states although some honeycomb systems host large band gaps. By employing tight-binding model analysis, we have summarized two types of topologically trivial states: one is due to the coexistence of quadratic non-Dirac and linear Dirac bands in the same spin channel that act together destructively in magnetic materials (such as, CrBr3, CrCl3, and VBr3 monolayers); the other one is caused by the destructive coupling effect between two different spin channels due to small magnetic spin splitting in heavy-metal-based materials, such as, BaTe(111)-supported plumbene. Further investigations reveal that topologically nontrivial states can be realized by removing the Dirac band dispersion of the magnetic monolayers for the former case (such as in alkali metal doped CrBr3), while separating the two different spin channels from each other by enhancing the magnetic spin splitting for the latter case (such as in half-iodinated silicene). Thus, our work provides a theoretical guideline to manipulate the topological states in a two-dimensional honeycomb lattice.

Coordination-induced bond weakening in NiC3: An experimental and theoretical investigation.

Mass-selected photoelectron velocity-map imaging spectroscopy in conjunction with the density functional theory calculations was employed to investigate the geometrical and chemical bonding properties of NiC3-/0. Both the photoelectron spectrum and photoelectron angular distribution were measured from the spectra, yielding useful geometrical and electronic information about NiC3-/0. The complementary theoretical calculations suggest that the linear and fan-like structures were both populated experimentally in the cluster beam. Further comparative study on the synergistic donor-acceptor interactions in both isomers revealed the side-on coordination-induced bond weakening in the fan-like isomer as compared to the linear isomer. These findings will shed light on the structure-dependent reactivity of transition metal carbides.

Carbonaceous Material Modified MoO2 Nanospheres with Oxygen Vacancies for Enhanced Visible-Light Photocatalytic Oxidative Coupling of Benzylamine.

Surface oxygen vacancy (OV) plays a pivotal role in the activation of molecular oxygen and separation of electrons and holes in photocatalysis. Herein, carbonaceous materials-modified MoO2 nanospheres with abundant surface OVs (MoO2/C-OV) were successfully synthesized via glucose hydrothermal processes. In situ introduction of carbonaceous materials triggered a reconstruction of the MoO2 surface, which introduced abundant surface OVs on the MoO2/C composites. The surface oxygen vacancies on the obtained MoO2/C-OV were confirmed via electron spin resonance spectroscopy (ESR) and X-ray photoelectron spectroscopy (XPS). The surface OVs and carbonaceous materials boosted the activation of molecular oxygen to singlet oxygen (1O2) and superoxide anion radical (•O2-) in selectively photocatalytic oxidation of benzylamine to imine. The conversion of benzylamine was 10 times that of pristine MoO2 nanospheres with a high selectivity under visible light irradiation at 1 atm air pressure. These results open an avenue to modify Mo-based materials for visible light-driven photocatalysis.

Tuning the Site-to-Site Interaction of Heteronuclear Diatom Catalysts MoTM/C2N (TM = 3d Transition Metal) for Electrochemical Ammonia Synthesis.

Ammonia (NH3) synthesis is one of the most important catalytic reactions in energy and chemical fertilizer production, which is of great significance to the sustainable development of society and the economy. The electrochemical nitrogen reduction reaction (eNRR), especially when driven by renewable energy, is generally regarded as an energy-efficient and sustainable process to synthesize NH3 in ambient conditions. However, the performance of the electrocatalyst is far below expectations, with the lack of a high-efficiency catalyst being the main obstacle. Herein, by means of comprehensive spin-polarized density functional theory (DFT) computations, the catalytic performance of MoTM/C2N (TM = 3d transition metal) for use in eNRR was systematically evaluated. Among the results, MoFe/C2N can be considered the most promising catalyst due to its having the lowest limiting potential (-0.26 V) and high selectivity in the context of eNRR. Compared with its homonuclear counterparts, MoMo/C2N and FeFe/C2N, MoFe/C2N can balance the first protonation step and the sixth protonation step synergistically, showing outstanding activity regarding eNRR. Our work not only opens a new door to advancing sustainable NH3 production by tailoring the active sites of heteronuclear diatom catalysts but also promotes the design and production of novel low-cost and efficient nanocatalysts.

Immobilized triatomic CuB2 clusters on 2D carbon nitride: highly selective conversion of CO to ethanol at low potentials.

A promising pathway for carbon usage and energy storage is electrocatalytic reduction of CO to form high-value multi-carbon products. Herein, the d-p coupled triatomic catalyst CuB2@g-C3N4 with significant activity and selectivity for ethanol is presented for the first time. Density functional theory calculations elucidate that these spatially confined triatomic centers are capable of immobilizing multiple CO molecules, providing an exclusive reaction channel for direct C-C coupling. The CuB2@g-C3N4 catalyst can effectively reduce the energy barrier of CO dimerization to 0.46 eV. The limiting potential is only -0.19 V, which is much smaller than that of other Cu-based catalysts. Additionally, the CuB2@g-C3N4 catalyst can effectively inhibit the generation of competing C1 products and hydrogen evolution reactions. Excitingly, CuB2 loading makes g-C3N4 more optically active in visible and even infrared light. This work provides important ideas for the atomically precise design of novel d-p coupled catalysts for the direct conversion of CO2/CO into energetic fuels and high-value chemicals.