Sublayer-Sulfur-Vacancy-Induced Charge Redistribution of FeCuS Nanoflower Awakening Alkaline Hydrogen Evolution.

Advancing the progress of sustainable and green energy technologies requires the improvement of valid electrocatalysts for the hydrogen evolution reaction (HER). Reconfiguring charge distribution through heteroatom doping-induced vacancy serves as an effective approach to implement high performance for HER catalysts. Here, we successfully fabricated Fe-doped CuS (FeCuS) with the sublayer sulfur vacancy to judge its HER performance and dissect the activity origins. Density functional theory calculation further elucidates that the primary factor contributing to the heightened HER activity is that the sublayer sulfur vacancies awaken the charge redistribution. In addition to effectively decreasing the energy barrier associated with the Volmer step, it modulates the adsorption/desorption capacity of H*. As a result, its intrinsic activity for the HER has significantly increased. Concretely, the obtained FeCuS displays an excellent catalytic performance, whose Tafel slope is only 59 mV dec-1 and the overpotential (at 10 mA cm-2) is as low as 71 mV in an alkaline environment, surpassing the majority of previously documented catalysts in scientific literature. This work shows that the construction of sublayer sulfur vacancies by Fe doping can achieve the charge redistribution and precise tuning of electronic structure; thereby, the inert CuS can be transformed into highly efficient electrocatalysts.

FeCoCuMnRuB Nanobox with Dual Driving of High-Entropy and Electron-Trap Effects as the Efficient Electrocatalyst for Water Oxidation.

High-entropy borides hold potential as electrocatalysts for water oxidation. However, the synthesis of the tailored nanostructures remains a challenge due to the thermodynamic immiscibility of polymetallic components. Herein, a FeCoCuMnRuB nanobox decorated with a nanosheet array was synthesized for the first time by a "coordination-etch-reduction" method. The FeCoCuMnRuB nanobox has various structural characteristics to express the catalytic performance; meanwhile, it combines the high-entropy effect of multiple components with the electron trap effect induced by electron-deficient B, synergistically regulating its electronic structure. As a result, FeCoCuMnRuB nanobox exhibits enhanced OER activity with a low overpotential (η10 = 233 mV), high TOF value (0.0539 s-1), small Tafel slope (61 mV/dec), and a satisfactory stability for 200 h, outperforming the high-entropy alloy and low-entropy borides. This work develops a high entropy and electron-deficient B-driven strategy for motivating the catalytic performance of water oxidation, which broadens the structural diversity and category of high-entropy materials.

A graphene/Janus B2P6 heterostructure with a controllable Schottky barrier via interlayer distance and electric field.

Lowering the Schottky barrier at the metal-semiconductor interface remains a stern challenge in the field of field-effect transistors. Herein, an in-depth investigation was conducted to explore the formation mechanism of the Schottky barrier via interlayer distance and external electric field, utilizing the first-principles approach. Attributed to the vertical asymmetric structure of B2P6, ohmic contact forms at the interface of a graphene/B2P6(001) heterostructure, and an n-type Schottky contact with a Schottky barrier of 0.51 eV forms at the interface of a graphene/B2P6(001̄) heterostructure. Furthermore, the Schottky barrier height and the contact type can be changed by adjusting the interlayer spacing or applying an electric field along the Z direction. A high carrier concentration of 4.65 × 1013 cm-2 is obtained in the graphene/B2P6(001) heterostructure when an external electric field of 0.05 V Å-1 is applied. Verifiably, alterations in the energy band structure are attributed to the redistribution of charges at the interface. The new findings indicate that GR/B2P6 heterostructures are a key candidate for next-generation Schottky field-effect transistor development.

Liquid metal assisted fabrication of MXene-based films: Toward superior electromagnetic interference shielding and thermal management.

The development of thin and flexible films that possess both electromagnetic interference (EMI) shielding and thermal management capabilities has always been an intriguing pursuit, but itisnevertheless a crucialproblemtoaddress. Inspired by the deformability of liquid metal (LM) and film forming capacity of MXene, here we present a series of ternary compositing films prepared via cellulose nanofiber (CNF) assisted vacuum filtration technology. Originating from the highly conductive LM/MXene network, the MLMC film presents a maximum EMI shielding effectiness (EMI SE) of 78 dB at a tiny thickness of 45 µm, together with a high specific EMI SE of 3046 dB mm-1. Meanwhile, these compositing films also deliver excellent flexibility and mechanical reliability, showing no obvious decline in EMI shielding performance even after 1000 bending and 500 folding cycles, respectively. Moreover, notable anisotropic thermal conductive property was successfully achieved, allowing for a highly desirable in-plane thermal conductivity of 7.8 W m-1 K-1. This accomplishment also yielded an exceptional electro-thermal conversion capacity, enabling efficient low-voltage (3 V) heating capabilities. These captivating features are expected to greatly drive the widespread adoption of LM-based films in future flexible electronic and wearable technologies.

Novel Janus MoSiGeN4 nanosheet: adsorption behaviour and sensing performance for NO and NO2 gas molecules.

A novel Janus MoSiGeN4 nanosheet is proposed for detecting poisonous gas molecules. Herein, the adsorption behaviour and sensing performance of both sides of the MoSiGeN4 monolayer to NO and NO2 gas molecules were investigated by first-principles calculations. Firstly, it is found that the MoSiGeN4 monolayer exhibits structural stability and indirect gap semiconductor characteristics. The largest adsorption energy of NO2 molecules on the MoSiGeN4 monolayer is -0.24 eV, which is higher than the -0.13 eV for NO molecules. Of course, the physisorption between gas molecules and the MoSiGeN4 monolayer appears with slight charge transfer. It is confirmed that NO molecules and NO2 molecules act as electron donors and electron acceptors, respectively. Meanwhile, the generation of small band gaps and impurity levels in the electronic structures after gas adsorption is in favour of the enhancement of electronic conductivity. Furthermore, the longest recovery times of NO and NO2 molecules are predicted to be 0.15 and 10.67 ns at room temperature, and the lateral diffusion at the surface requires crossing a large energy barrier. These findings provide indisputable evidence for further design and fabrication of highly sensitive gas sensors based on the MoSiGeN4 monolayer.

Synergetic effect of photocatalysis and peroxymonosulfate activated by MFe2O4 (M = Co, Mn, or Zn) for enhanced photocatalytic activity under visible light irradiation.

Nanosized MFe2O4 (M = Co, Mn, or Zn) photocatalysts were synthesized via a simple sol-gel method. MFe2O4 photocatalysts exhibited lower photocatalytic activity for the degradation of levofloxacin hydrochloride under visible light irradiation. For enhancement of photocatalytic activity, MFe2O4 was used to activate peroxymonosulfate and degrade levofloxacin hydrochloride under visible light irradiation. The influences of peroxymonosulfate dosage, levofloxacin hydrochloride concentration, pH value, and temperature on peroxymonosulfate activation to degrade levofloxacin hydrochloride were investigated in detail. The mechanism of activation of peroxymonosulfate by MFe2O4 was proposed and proved by radical quenching experiments, electron spin resonance analysis, X-ray photoelectron spectroscopy, electrochemical impedance spectroscopy, and transient photocurrent responses. The combined activation effects of photogenerated e-/h+ and transition metals on peroxymonosulfate to produce sulfate radical clearly enhanced the degradation efficiency.

Defective ultra-thin two-dimensional g-C3N4 photocatalyst for enhanced photocatalytic H2 evolution activity.

The two-dimensional semiconductor photocatalytic material has excellent photocatalytic H2 evolution activity. In order to further improve the hydrogen production activity of g-C3N4, this study improved the preparation process of g-C3N4 and obtained a new photocatalyst (name H-CN) with a higher absorption range, larger specific surface area, and faster hydrogen production activity. Compared with the originally prepared g-C3N4, the H-CN absorption range has been improved, and the utilization of visible light has reached 650 nm. When the doping amount of Pt cocatalyst was 1.0 wt%, the H-CN demonstrates excellent photocatalytic hydrogen production activity, with a hydrogen production rate of 4.3 mmol h-1·g-1, which was 7.0 times higher than that pure 1.0 wt% Pt/g-C3N4. The fluorescence spectroscopy of H-CN showed better separation of carriers and longer lifetime. This study has guiding significance for the preparation of subsequent ultra-thin nanosheet photocatalysts and the establishment of high-efficiency photocatalytic systems.

Interfacial internal electric field and oxygen vacancies synergistically enhance photocatalytic performance of bismuth oxychloride.

Solar-to-chemical energy conversion is valuable and sustainable strategy for energy and environmental crisis through photocatalysis. The amorphous SnOx modified BiOCl (Sn-BiOCl) full-spectrum-responsive catalysts were designed and synthesized through solvothermal method. The introduced Sn regulates the growth of BiOCl to form ultrathin nanosheets with surface oxygen vacancies. And the surface modification of SnOx induces interfacial internal electric field via charge redistribution on the interface of BiOCl and SnOx to accelerate the photogenerated charge separation. The modification of SnOx decreased work function of Sn-BiOCl and thus elevated its conduction band and valence band simultaneously, leading enhanced photocatalytic reducibility with the improved generation rate of ·O2-. The surface SnOx and oxygen vacancies of Sn-BiOCl broadened light absorption range and enhanced photocatalytic performance synergistically, resulting in 14-fold increased photodegradation rate of phenol compared with pure BiOCl under full spectrum. This method is also able to expand to other metal ions (such as Fe3+, In3+ and Sb3+). This work provides a valuable concept in structure regulating for enhanced photocatalytic performance in the removal of organic pollutants by interfacial internal electric field and surface oxygen vacancies.

Insights into the mechanism of the enhanced visible-light photocatalytic activity of a MoS2/BiOI heterostructure with interfacial coupling.

An understanding of the high photocatalytic performance reported for MoS2/BiOI nanocomposite is far from satisfactory. Here, the interfacial interaction and electronic properties of a MoS2/BiOI heterostructure were investigated systematically for the first time by first-principle calculations incorporating a semi-empirical dispersion-correction scheme. Our results confirm the reasonable existence of van der Waals interactions and a favorable Z-scheme mechanism, based on the typical interfacial cohesive energy and the energy level lineup at the interface. Analyzing the charge density differences and work functions, the built-in electric field is formed along the direction from MoS2 to BiOI after the interface equilibrium, and facilitates the separation of photoinduced electron-hole pairs in the interface. Additionally, it can be inferred that the incorporation of MoS2 into BiOI increases the carrier mobility and improves light harvesting, in agreement with the previously reported experimental data. Our work provides an insight into the mechanism of the enhanced visible-light photocatalytic activity of a MoS2/BiOI heterostructure, and helps to design other new heterostructure combinations.

CoNiO2 as a novel water oxidation cocatalyst to enhance PEC water splitting performance of BiVO4.

A strategy is proposed for modifying BiVO4 photoanode with CoNiO2 as a novel water oxidation cocatalyst to enhance PEC water splitting performance. The results show that CoNiO2 has the following functions: reducing photogenerated charge recombination centers; providing trapping sites to promote charge separation; improving the stability of the overall system; providing more active sites; and offering a lower overpotential. The BiVO4/CoNiO2 photoanode has a higher photocurrent density (1.16 mA cm-2 at 1.23 V vs. RHE), a lower onset potential (∼0.06 V vs. RHE), a larger IPCE (34.37%) and ABPE (0.163%), better stability and good rates of hydrogen evolution (0.0148 µmol cm-2 min-1) and oxygen evolution (0.0076 µmol cm-2 min-1). The strategy provides promising prospects for achieving efficient PEC water splitting performance using water oxidation cocatalysts.

Large dipole moment induced efficient bismuth chromate photocatalysts for wide-spectrum driven water oxidation and complete mineralization of pollutants.

Herein, a wide-spectrum (∼678 nm) responsive Bi8(CrO4)O11 photocatalyst with a theoretical solar spectrum efficiency of 42.0% was successfully constructed. Bi8(CrO4)O11 showed highly efficient and stable photocatalytic water oxidation activity with a notable apparent quantum efficiency of 2.87% (420 nm), superior to many reported wide-spectrum driven photocatalysts. Most remarkably, its strong oxidation ability also enables the simultaneous degradation and complete mineralization for phenol, and its excellent performance is about 23.0 and 2.9 times higher than CdS and P25-TiO2, respectively. Its high activity is ascribed to the giant internal electric field induced by its large crystal dipole, which accelerates the rapid separation of photogenerated electron-hole pairs. Briefly, the discovery of wide-spectrum bismuth chromate and the mechanism of exponentially enhanced photocatalytic performance by increasing the crystal dipole throw light on improving solar energy conversion.

Novel recyclable BiOBr/Fe3O4/RGO composites with remarkable visible-light photocatalytic activity.

Magnetic BiOBr/Fe3O4/RGO composites with remarkable photocatalytic capability were prepared by a simple hydrothermal method to load 3D flower-like microspherical BiOBr onto the surface of Fe3O4/RGO. Under visible-light irradiation (λ > 420 nm), the BiOBr/Fe3O4/RGO composite with 56% mass percentage of Fe3O4/RGO shows the optimal removal ability for Rhodamine B, and the total removal efficiency is 96%. The coupling of Fe3O4/RGO and BiOBr elevates the conduction band of BiOBr, which enhances the reduction level of BiOBr/Fe3O4/RGO composites. Ultimately, based on experiments and theoretical calculations, an n-type Schottky contact formed at the heterojunction interface between RGO doped with Fe3O4 and BiOBr is proposed for photoexcited charge transfer. The RGO with great adsorptivity plays a major role in the photocatalysts composed of BiOBr, RGO and Fe3O4. Further, BiOBr/Fe3O4/RGO composites with permanent-magnetism can be recovered and reused easily by external magnetic field and maintain a total removal efficiency of 90% after four cycles.

Surface-Electron Coupling for Efficient Hydrogen Evolution.

Maximizing the activity of materials towards the alkaline hydrogen evolution reaction while maintaining their structural stability under realistic working conditions remains an area of active research. Herein, we report the first controllable surface modification of graphene(G)/V8 C7 heterostructures by nitrogen. Because the introduced N atoms couple electronically with V atoms, the V sites can reduce the energy barrier for water adsorption and dissociation. Investigation of the multi-regional synergistic catalysis on N-modified G/V8 C7 by experimental observations and density-functional-theory calculations reveals that the increase of electron density on the epitaxial graphene enable it to become favorable for H* adsorption and the subsequent reaction with another H2 O molecule. This work extends the range of surface-engineering approaches to optimize the intrinsic properties of materials and could be generalized to the surface modification of other transition-metal carbides.

Hydrothermal synthesis of Bi2WO6 with a new tungsten source and enhanced photocatalytic activity of Bi2WO6 hybridized with C3N4.

Bi2WO6 nanosheets were synthesized by a hydrothermal method with H2WO4 for the first time. The band structure of Bi2WO6 was investigated on the basis of density functional theory calculations. Bi2WO6 photocatalysts showed photocatalytic activity for the degradation of methylene blue under visible light irradiation. Kinetic studies using radical scavenger technologies suggested that holes were the dominant photo-oxidants. After hybridization with C3N4, the photocatalytic activity of Bi2WO6 was obviously enhanced. The enhanced photocatalytic activity of the C3N4/Bi2WO6 photocatalysts could be attributed to the effective separation of photogenerated e-/h+ pairs. The photogenerated holes on the valence band of Bi2WO6 can transfer to the highest occupied molecular orbital of C3N4via the well-developed interface, causing a reduction in the probability of e-/h+ recombination; consequently, large numbers of photogenerated holes led to the enhancement of the photocatalytic activity.

Controlling electronic properties of MoS2/graphene oxide heterojunctions for enhancing photocatalytic performance: the role of oxygen.

The manipulation of the constituents of novel hetero-photocatalysts is an effective method for improving photocatalytic efficiency, but a theoretical understanding of the relationship between interlayer interaction and photocatalytic activity is still lacking. Herein, the interfacial interactions and electronic properties of MoS2/graphene oxide (GO) heterojunctions with various O concentrations were explored systematically by first-principles calculations. The results indicate that MoS2 and GO can form a stable van der Waals heterojunction, and enhance the built-in internal electric field from GO to the MoS2 surface with the increase in O concentration after interfacial equilibrium. It is inferred that the photogenerated electrons and holes naturally accumulate in the conduction band of GO and the valence band of MoS2, respectively, under the built-in internal electric field driving, indicating the formation of direct Z-scheme heterojunctions. In addition, a red shift of the light absorption edge and the shift up of the conduction band edge of MoS2/GO heterojunctions are observed with an increase in O concentration. It can be concluded that the O atom plays a crucial role in the energy band alignment of MoS2/GO heterojunctions for the improvement of photocatalytic performance. These results are beneficial to understand and design layered MoS2/GO photocatalytic systems or as cocatalysts with other semiconductors.

Probing π-π stacking modulation of g-C3N4/graphene heterojunctions and corresponding role of graphene on photocatalytic activity.

The photoelectrochemical properties of g-C3N4 sheet are modified by the π-π stacking interaction with graphene, and the corresponding role of graphene on the surface chemical reactions is investigated by density functional theory. The calculated cohesive energies and the lattice mismatch energies indicate that g-C3N4 and graphene are in parallel contact and can form a stable heterojunction. According to our calculated energy band structures and work functions of g-C3N4/graphene heterojunctions, the band edge modulations by graphene are discussed and corresponding photoinduced charge transfer processes are analyzed in detail. It is found that the incorporating of graphene into g-C3N4 facilitates the separation of photoinduced e-/h+ pairs and the oxidation capacity enhancement of the photoinduced holes with the downshifting of the valence band edge of g-C3N4 layer. It is identified that the inhomogeneous onsite energies between interlayer and the band edge modulations are induced by the inhomogeneous charge redistribution between interlayer caused by graphene. Further, the initial dynamic reaction processes of oxygen atoms in g-C3N4/graphene heterojunctions also confirm the significant role of graphene on the surface chemical reactions.

Ultrathin TiO2(B) Nanosheets as the Inductive Agent for Transfrering H2O2 into Superoxide Radicals.

A reflux method to synthesize ultrathin polycrystalline TiO2(B) nanosheets (NSs) which are assembled by single crystals, and further stacked into nanoflower structures, is described. On the basis of the theoretical calculations and experiments, H2O2 can easily substitute the ethylene glycol adsorbed on the surface of TiO2(B) NSs, forming H2O2-NS due to the lower adsorption energy and the unique structural features of ultrathin TiO2(B) nanosheets. TiO2(B) NSs and the H2O2 system can be accelerated to generate superoxide radicals under heat or light and thus exhibit a great degradation property on dye molecules; the total organic carbon (TOC) removal rate was 6 times higher than that for H2O2 alone. Meanwhile, TiO2(B) NSs and the H2O2 system have a good application on the selective oxidation due to the reactive species of superoxide radicals avoiding overoxidization of benzyl alcohol. The conversion of benzyl alcohol oxidized to benzaldehyde in water solution under low temperature and atmospheric pressure was 51.13%, while the selectivity was close to 100%. We believe that the present findings will provide valuable methods for highly efficient generation of superoxide radicals and broaden their applications in catalysis.

Synthesis of CdWO4 nanorods and investigation of the photocatalytic activity.

CdWO4 nanorod photocatalysts were synthesized by a hydrothermal method. CdWO4 nanorod photocatalysts showed highly efficient photocatalytic activity for the degradation of methylene blue under ultraviolet light irradiation. On the basis of the experiment results, the difference in photocatalytic activities of the samples was mainly attributed to surface area, surface hydroxyl groups and defects which can act as inactivation centers. Kinetic studies using radical scavenger technologies suggested that OH˙ radicals were the dominant photooxidants.