Structurally disordered MoSe2 with rich 1T phase as a universal platform for enhanced photocatalytic hydrogen production.

The improvement of surface reactivity in noble-metal-free cocatalysts is crucial for the development of efficient and cost-effective photocatalytic systems. However, the influence of crystallinity on catalytic efficacy has received limited attention. Herein, we report the utilization of structurally disordered MoSe2 with abundant 1T phase as a versatile cocatalyst for photocatalytic hydrogen evolution. Using MoSe2/carbon nitride (CN) hybrids as a case study, it is demonstrated that amorphous MoSe2 significantly enhances the hydrogen evolution rate of CN, achieving up to 11.37 µmol h-1, surpassing both low crystallinity (8.24 µmol h-1) and high crystallinity MoSe2 (3.86 µmol h-1). Experimental analysis indicates that the disordered structure of amorphous MoSe2, characterized by coordination-unsaturated surface sites and a rich 1T phase with abundant active sites at the basal plane, predominantly facilitates the conversion of surface-bound protons to hydrogen. Conversely, the heightened charge transfer capacity of the highly crystalline counterpart plays a minor role in enhancing practical catalytic performance. This approach is applicable for enhancing the photocatalytic hydrogen evolution performance of various semiconducting photocatalysts, including CdS, TiO2, and ZnIn2S4, thereby offering novel insights into the advancement of high-performance non-precious catalysts through phase engineering.

Na-mediated carbon nitride realizing CO2 photoreduction with selectivity modulation.

The depressed directional separation of photogenerated carriers and weak CO2 adsorption/activation activity are the main factors hampering the development of artificial photosynthesis. Herein, Na ions are embedded in graphitic carbon nitride (g-C3N4) to achieve directional migration of the photogenerated electrons to Na sites, while the electron-rich Na sites enhance CO2 adsorption and activation. Na/g-C3N4 (NaCN) shows improved photocatalytic reduction activity of CO2 to CO and CH4, and under simulated sunlight irradiation, the CO yield of NaCN synthesized by embedding Na at 550°C (NaCN-550) is 371.2 µmol g-1 h-1, which is 58.9 times more than that of the monomer g-C3N4. By means of theoretical calculations and experiments including in situ fourier transform infrared spectroscopy, the mechanism is investigated. This strategy which improves carrier separation and reduces the energy barrier at the same time is important to the development of artificial photosynthesis.

Co single atom coupled oxygen vacancy on W18O49 nanowires surface to construct asymmetric active site enhanced peroxymonosulfate activation.

Enhancing the activation of peroxymonosulfate (PMS) is essential for generating more reactive oxygen species in advanced oxidation process (AOPs). Nevertheless, improving PMS adsorption and expediting interfacial electron transfer to enhance reaction kinetics pose significant challenges. Herein, we construct confined W18O49 nanowires with asymmetric active centers containing Co-Vo-W (Vo: oxygen vacancy). The design incorporates surface-rich Vo and single-atom Co, and the resulting material is employed for PMS activation in water purification. By coupling unsaturated coordinated electrons in Vo with low-valence Co single atoms to construct an the "electron fountainhead", the adsorption and activation of PMS are enhanced. This results in the generation of more active free radicals (SO4•-, •OH, •O2-) and non-free radicals (1O2) for the decomposition of micropollutants. Thereinto, the degradation rate of bisphenol A (BPA) by Co-W18O49 is 32.6 times faster that of W18O49 monomer, which is also much higher than those of other transition-metal-doped W18O49 composites. This work is expected to help to elucidate the rational design and efficient PMS activation of catalysts with asymmetric active centers.

Engineering the Sulfide Semiconductor/Photoinactive-MOF Heterostructure with a Hollow Cuboctahedral Structure to Enhance Photocatalytic CO2-Epoxide-Cycloaddition Efficiency.

Providing efficient electronic transport channels has always been a promising strategy to mitigate the recombination of photogenerated charge carriers. In this study, a heterostructure composed of a semiconductor/photoinactive-metal-organic framework (MOF) was constructed to provide innovative channels for electronic transport. Prepared using a previously reported method ( Angew. Chem., Int. Ed. 2016, 55, 15301-15305) with slight modifications to temperature and reaction time, the CuS@HKUST-1 hollow cuboctahedron was synthesized. The CuS@HKUST-1 heterostructure possessed a well-defined cuboctahedral morphology with a uniform size of about 500 nm and a hollow structure with a thickness of around 50 nm. The CuS nanoparticles were uniformly distributed on the HKUST-1 shell. Structural characterization in cooperation with density functional theory (DFT) calculations revealed that CuS can effectively transfer photogenerated electrons to HKUST-1. CuS@HKUST-1 hollow cuboctahedrons were first introduced to the photocatalytic cycloaddition reaction of CO2 with epoxides, demonstrating excellent photocatalytic activity and stability at mild conditions (room temperature, solvent-free, and 1 atm CO2 pressure). The high photocatalytic performance of the CuS@HKUST-1 hollow cuboctahedron could be attributed to (1) the unique hollow cuboctahedron morphology, which provided a large specific surface area (693.1 m2/g) and facilitated the diffusion and transfer of reactants and products; and (2) CuS@HKUST-1 providing electronic transport channels from CuS to HKUST-1, which could enhance the adsorption and activation of CO2. Cu2+ carrying surplus electrons can activate CO2 to CO2-. The charge separation and transfer in the photocatalytic process can also be effectively promoted. This work provides a cost-effective and environmentally friendly approach for CO2 utilization reactions under ambient conditions, addressing the critical issue of rising atmospheric CO2 levels.

Adsorption Behavior of Organoarsenicals over MnFe2O4-Graphene Hybrid Nanocomposite: The Role of Organoarsenic Chemical Structures.

As a kind of emerging contaminant, organoarsenic compounds have drawn wide concern because of their considerable solubilities in water, and the highly toxic inorganic arsenic species formed during their biotic and abiotic degradation in the natural environment. Thus, the effective removal and studying of the adsorption mechanism of organoarsenic compounds are of significant urgency. In this work, MnFe2O4 and MnFe2O4/graphene were prepared through a facile solvothermal method. From the results of the Transmission Electron Microscope (TEM) characterization, it can be found that MnFe2O4 nanoparticles were uniformly distributed on the surface of the graphene. And the specific surface area of the MnFe2O4/graphene was about 146.39 m2 g-1, much higher than that of the MnFe2O4 (86.15 m2 g-1). The interactions between organoarsenic compounds and adsorbents were conducted to study their adsorption behavior and mechanism. The maximum adsorption capacities of MnFe2O4/graphene towards p-arsanilic acid (p-ASA) and roxarsone (ROX) were calculated to be 22.75 and 30.59 mg g-1. Additionally, the ionic strength, negative ions, and humus were introduced to investigate the adsorption performance of organoarsenic compounds. Electrostatic adsorption and surface complexation are the primary adsorption mechanisms on account of X-ray photoelectron spectroscopy (XPS) and the Fourier-transform infrared spectroscopy (FT-IR) analysis. This research extends the knowledge into studying the interaction between organoarsenic species and hybrid nanomaterials in the natural environment.

Piezo-photocatalysis for efficient charge separation to promote CO2 photoreduction in nanoclusters.

The substantial emissions of CO2 greenhouse gases have resulted in severe environmental problems, and research on the implementation of semiconductor materials to minimize CO2 is currently a highly discussed subject. Effective separation of interface charges is a major challenge for efficient piezo-photocatalytic systems. Meanwhile, the ultrasmall-sized metal nanoclusters can shorten the distance of electron transport. Herein, we synthesized Au25(p-MBA)18 nanoclusters (Au25 NCs) modified red graphitic carbon nitride (RCN) nanocatalysts with highly exposed Au active sites by in-situ seed growth method. The loading of Au25 NCs on the RCN surface provides more active sites and creates a long-range ordered electric field. It allows for the direct utilization of the piezoelectric field to separate photogenerated carriers during photo-piezoelectric excitation. Based on the above advantages, the rate of CO2 reduction to CO over Au25 NCs/RCN (111.95 µmol g-1 h-1) was more than triple compared to that of pristine RCN. This paper has positive implication for further application of metal clusters loaded semiconductor for piezo-photocatalytic CO2 reduction.

Ni-modified FeOOH integrated electrode by self-source corrosion of nickel foam for high-efficiency electrochemical water oxidation.

The construction and application of efficient iron oxyhydroxide (FeOOH) is still a challenge in the field of energy conversion. Here, a facile preparation method is developed by directly utilizing commercialized nickel foams (NF) as the nickel source and the supporting framework, as well as the ingenious use of etching effect originating from acidic medium in the process of iron salt hydrolysis. As a result, a Ni-modulated FeOOH integrated electrode (Ni-FeOOH/NF) is obtained. Unexpectedly, the implementation of our scheme effectively activates the catalytic intrinsic activity of FeOOH, successfully transforming the inert NF into an integrated electrode with high oxygen evolution reaction (OER) performance. Specifically, the Ni-FeOOH/NF exhibits the overpotential of 277 mV (@100 mA cm-2) and superior stability for OER. Additionally, the as-prepared Ni-FeOOH/NF electrode could also operate steadily for OER in alkaline adjusted saline water. Our research provides a new idea for the preparation of satisfactory Fe-based metal materials as OER electrocatalysts.

Recent Advances in Phase-Engineered Photocatalysts: Classification and Diversified Applications.

Phase engineering is an emerging strategy for tuning the electronic states and catalytic functions of nanomaterials. Great interest has recently been captured by phase-engineered photocatalysts, including the unconventional phase, amorphous phase, and heterophase. Phase engineering of photocatalytic materials (including semiconductors and cocatalysts) can effectively affect the light absorption range, charge separation efficiency, or surface redox reactivity, resulting in different catalytic behavior. The applications for phase-engineered photocatalysts are widely reported, for example, hydrogen evolution, oxygen evolution, CO2 reduction, and organic pollutant removal. This review will firstly provide a critical insight into the classification of phase engineering for photocatalysis. Then, the state-of-the-art development of phase engineering toward photocatalytic reactions will be presented, focusing on the synthesis and characterization methodologies for unique phase structure and the correlation between phase structure and photocatalytic performance. Finally, personal understanding of the current opportunities and challenges of phase engineering for photocatalysis will also be provided.

Carbon Quantum Dots Accelerating Surface Charge Transfer of 3D PbBiO2I Microspheres with Enhanced Broad Spectrum Photocatalytic Activity-Development and Mechanism Insight.

The development of a highly efficient, visible-light responsive catalyst for environment purification has been a long-standing exploit, with obstacles to overcome, including inefficient capture of near-infrared photons, undesirable recombination of photo-generated carriers, and insufficient accessible reaction sites. Hence, novel carbon quantum dots (CQDs) modified PbBiO2I photocatalyst were synthesized for the first time through an in-situ ionic liquid-induced method. The bridging function of 1-butyl-3-methylimidazolium iodide ([Bmim]I) guarantees the even dispersion of CQDs around PbBiO2I surface, for synchronically overcoming the above drawbacks and markedly promoting the degradation efficiency of organic contaminants: (i) CQDs decoration harness solar photons in the near-infrared region; (ii) particular delocalized conjugated construction of CQDs strength via the utilization of photo-induced carriers; (iii) π-π interactions increase the contact between catalyst and organic molecules. Benefiting from these distinguished features, the optimized CQDs/PbBiO2I nanocomposite displays significantly enhanced photocatalytic performance towards the elimination of rhodamine B and ciprofloxacin under visible/near-infrared light irradiation. The spin-trapping ESR analysis demonstrates that CQDs modification can boost the concentration of reactive oxygen species (O2•-). Combined with radicals trapping tests, valence-band spectra, and Mott-Schottky results, a possible photocatalytic mechanism is proposed. This work establishes a significant milestone in constructing CQDs-modified, bismuth-based catalysts for solar energy conversion applications.

Integration of biochar into Ag3PO4/α-Fe2O3 heterojunction for enhanced reactive oxygen species generation towards organic pollutants removal.

A biochar (BC) harbored Ag3PO4/α-Fe2O3 type-Ⅰ heterojunction (Ag-Fe-BC) was prepared by a hydrothermal-impregnation method to transfer active center of heterojunctions. The electrochemical and spectroscopic tests demonstrated that BC enhanced the catalytic performance of the heterojunction by enhancing photocurrent, reducing fluorescence intensity, and facilitating separation of electron-hole pairs. The photocatalytic activity showed the Ag-Fe-BC (5:1:3) could degrade Rhodamine B (20 mg/L) by up to 92.7%, which was 3.35 times higher than Ag3PO4/α-Fe2O3. Tetracycline and ciprofloxacin (20 mg/L) were degraded efficiently by 58.3% and 79.4% within 2 h, respectively. Electron paramagnetic resonance and scavenging experiments confirmed the major reactive oxygen species (ROS) consisted of singlet oxygen (1O2) and superoxide (·O2-). Excellent RhB adsorption and electrons capturing capacity of BC facilitated electron-hole pairs separation and ROS transferring to target organics followed by elevated degradation. Thus, a facile method was proposed to synthesize a highly efficient visible-light responsive photocatalyst for degradation of various organics in water.

Crystal phase engineering boosted photo-electrochemical kinetics of CoSe2 for oxygen evolution catalysis.

Crystal phase is an important parameter that can determine the electronic structure and catalytic properties of catalysts. In this work, we report the crystal phase dependent photo- and electrocatalytic oxygen evolution reaction (OER) performance of CoSe2. In electrocatalytic reaction, we firstly found that CoSe2 with orthorhombic phase (o-CoSe2) showed a higher OER performance than that of CoSe2 with cubic phase (c-CoSe2). In the further exploration of photocatalytic application using Fe2O3 as light harvester and CoSe2 as cocatalysts, o-CoSe2/Fe2O3 can realize the qualitative changes of photocatalytic oxygen evolution performance from "0″ to "1". As contrast, c-CoSe2/Fe2O3 cannot work in photocatalytic oxygen evolution process under the same condition. Experimental and theoretical analysis uncover that, the key factor leading to the crystal phase-dependent performance is the decreased activation barrier of H2O on o-CoSe2 surface. This work opens up an opportunity of correlating the CoSe2 crystal phase with performance in OER.

Accelerated Photoreduction of CO2 to CO over a Stable Heterostructure with a Seamless Interface.

Photocatalytic CO2 reduction is a means of alleviating energy crisis and environmental deterioration. In this work, a rising two-dimensional (2D) material rarely reported in the field of photocatalytic CO2 reduction, black phosphorus (BP) nanosheets, is synthesized, on which Co2P is in situ grown by solvothermal treatment using BP itself as a P source. Co2P on the BP nanosheets (BPs) surface can prevent the destruction of BPs in ambient air and, in the meantime, favor charge separation and CO2 adsorption and activation during the catalytic process. Upon light irradiation, Co2P can extract the photogenerated electrons effectively across the intimate interface and lower the CO2 activation energy barrier, supported by both experimental characterizations and theoretical calculations. Benefitting from integrated advantages of BPs and Co2P, the optimal Co2P/BPs exhibit photocatalytic reduction of CO2 to CO at a rate of 25.5 µmol g-1 h-1 with a selectivity of 91.4%, both of which are higher than those of pristine BPs. This work presents ideas for stabilizing BPs and improving their CO2 reduction performance simultaneously.

Controllable synthesized heterostructure photocatalyst Mo2C@C/2D g-C3N4: enhanced catalytic performance for hydrogen production.

Photocatalysis is a promising technology which can be applied in the fields of energy and environment. However, low charge separation efficiency has limited its commercial applications. In this work, we report a route to a controllable synthesized visible-light-driven heterostructure photocatalyst Mo2C@C/2D g-C3N4. The interfacial conductivity was improved by introducing Mo2C@C, which promoted the transportation of photogenerated carriers and suppressed their recombination. The optimal composite achieved a hydrogen (H2) generation rate of 2269.47 µmol g-1 h-1, and an external quantum efficiency (EQE) achieved 9.07% at λ = 405 nm. Thus, the great co-catalytic activity of Mo2C@C was unambiguously demonstrated.