p-Block Metal Based Single-Atom Catalysts Surpass Transition-Metal Counterparts in Photocatalytic H2O2 Production.

Growing interest in p-block metal single-atom catalysts (PM-SACs) is driven by their low toxicity, economic viability, and transition metal-like catalytic properties. However, selection criteria for p-block single-atom species and catalytic mechanisms of PM-SACs remain unclear. This study explores the catalytic abilities of PM-SACs and their transition metal counterparts (TM-SACs) based on polymetric carbon nitride (PCN) for photocatalytic hydrogen peroxide (H2O2) production. Using thermodynamic barriers as a key descriptor, it was found that PM-SACs can surpass TM-SACs in H2O2 production due to a lower energy barrier for *OOH intermediate formation resulting from optimized p-p hybridization. Specifically, Sb-SAC based on PCN shows the highest apparent quantum yield of 35.3% at 400 nm. This study offers a rationale for the utilization of p-block SACs in the context of sustainable chemical synthesis.

Oxygen Vacancy: How Will Poling History Affect Its Role in Photoelectrocatalysis.

Oxygen vacancy (VO) has been recognized to possess an effect to promote the charge separation and transfer (CST) in various n-type semiconductor based photoelectrodes. But how external stimulus will change this VO effect has not been investigated. In this work, external polarization is applied to investigate the effect of VO on the CST process of a typical ferroelectric BiFeO3 photoelectrode. It is found that negative poling treatment can significantly boost VO effect, while positive poling treatment will deteriorate the CST capability in BiFeO3 photoelectrodes. This poling history determined VO effect is rooted in the VO induced defect dipoles, wherein their alignment produces a depolarization electric field to modulate the CST driving force. This finding highlights the significance of poling history in functionalizing the VO in a photoelectrode.

Enzyme encapsulation in metal-organic frameworks using spray drying for enhanced stability and controlled release: A case study of phytase.

Encapsulating enzymes in metal-organic frameworks is a common practice to improve enzyme stability against harsh conditions. However, the synthesis of enzyme@MOFs has been primarily limited to small-scale laboratory settings, hampering their industrial applications. Spray drying is a scalable and cost-effective technology, which has been frequently used in industry for large-scale productions. Despite these advantages, its potential for encapsulating enzymes in MOFs remains largely unexplored, due to challenges such as nozzle clogging from MOF particle formation, utilization of toxic organic solvents, controlled release of encapsulated enzymes, and high temperatures that could compromise enzyme activity. Herein, we present a novel approach for preparing phytase@MIL-88 A using solvent-free spray drying. This involves atomizing two MOF precursor solutions separately using a three-fluid nozzle, with enzyme release controlled by manipulating defects within the MOFs. The physicochemical properties of the spray dried particles are characterized using X-ray diffraction, Fourier-transform infrared spectroscopy, and scanning electron microscopy. Leveraging the efficiency and scalability of spray drying in industrial production, this scalable encapsulation technique holds considerable promise for broad industrial applications.

Polarization Alignment in Polycrystalline BiFeO3 Photoelectrodes for Tunable Band Bending.

Polarization in a semiconductor can modulate the band bending via the depolarization electric field (EdP), subsequently tuning the charge separation and transfer (CST) process in photoelectrodes. However, the random orientation of dipole moments in many polycrystalline semiconductor photoelectrodes leads to negligible polarization effect. How to effectively align the dipole moments in polycrystalline photoelectrodes into the same direction to maximize the polarization is still to be developed. Herein, we report that the dipole moments in a ferroelectric BiFeO3 photoelectrode can be controlled under external poling, resulting in a tunable CST efficiency. A negative bias of -40 voltage (V) poling to the photoelectrode leads to an over 110% increase of the CST efficiency, while poling at +40 V, the CST efficiency is reduced to only 41% of the original value. Furthermore, a nearly linear relationship between the external poling voltage and surface potential is discovered. The findings here provide an effective method in tuning the band bending and charge transfer of the emerging ferroelectricity driven solar energy conversion.