Defects of Metal Halide Perovskites in Photocatalytic Energy Conversion: Friend or Foe?

Photocatalytic solar-to-fuel conversion over metal halide perovskites (MHPs) has recently attracted much attention, while the roles of defects in MHPs are still under debate. Specifically, the mainstream viewpoint is that the defects are detrimental to photocatalytic performance, while some recent studies show that certain types of defects contribute to photoactivity enhancement. However, a systematic summary of why it is contradictory and how the defects in MHPs affect photocatalytic performance is still lacking. In this review, the innovative roles of defects in MHP photocatalysts are highlighted. First, the origins of defects in MHPs are elaborated, followed by clarifying certain benefits of defects in photocatalysts including optical absorption, charge dynamics, and surface reaction. Afterward, the recent progress on defect-related MHP photocatalysis, i.e., CO2 reduction, H2 generation, pollutant degradation, and organic synthesis is systematically discussed and critically appraised, putting emphasis on their beneficial effects. With defects offering peculiar sets of merits and demerits, the personal opinion on the ongoing challenges is concluded and outlining potentially promising opportunities for engineering defects on MHP photocatalysts. This critical review is anticipated to offer a better understanding of the MHP defects and spur some inspiration for designing efficient MHP photocatalysts.

Approaches for Enhancing Wastewater Treatment of Photocatalytic Fuel Cells: A Review.

Environmental pollution and energy crises have garnered global attention. The substantial discharge of organic waste into water bodies has led to profound environmental contamination. Photocatalytic fuel cells (PFCs) enabling the simultaneous removal of refractory contaminants and recovery of the chemical energy contained in organic pollutants provides a potential strategy to solve environmental issues and the energy crisis. This review will discuss the fundamentals, working principle, and configuration development of PFCs and photocatalytic microbial fuel cells (PMFCs). We particularly focus on the strategies for improving the wastewater treatment performance of PFCs/PMFCs in terms of coupled advanced oxidation processes, the rational design of high-efficiency electrodes, and the strengthening of the mass transfer process. The significant potential of PFCs/PMFCs in various fields is further discussed in detail. This review is intended to provide some guidance for the better implementation and widespread adoption of PFC wastewater treatment technologies.

Slippery Porous-Liquid-Infused Porous Surface (SPIPS) with On-Demand Responsive Switching between "Defensive" and "Offensive" Antifouling Modes.

Slippery liquid-infused porous surfaces (SLIPS) have received widespread attention in the antifouling field. However, the reduction in antifouling performance caused by lubricant loss limits their application in marine antifouling. Herein, inspired by the skin of a poison dart frog which contains venom glands and mucus, a porous liquid (PL) based on ZIF-8 is prepared as a lubricant and injected into a silicone polyurethane (SPU) matrix to construct a new type of SLIPS for marine antifouling applications: the slippery porous-liquid-infused porous surface (SPIPS). The SPIPS consists of a responsive antifoulant-releasing switch between "defensive" and "offensive" antifouling modes to intelligently enhance the antifouling effect after lubricant loss. The SPIPS can adjust antifouling performance to meet the antifouling requirements under different light conditions. The wastage of antifoulants is reduced, thereby effectively maintaining the durability and service life of SLIPS materials. The SPIPS exhibits efficient lubricant self-replenishment, self-cleaning, anti-protein, anti-bacterial, anti-algal, and self-healing (97.48%) properties. Furthermore, it shows satisfactory 360-day antifouling performance in actual marine fields during boom seasons, demonstrating the longest antifouling lifespan in the field tests of reported SLIPS coatings. Hence, the SPIPS can effectively promote the development of SLIPS for neritic antifouling.

Metal-Based Electrocatalysts for Selective Electrochemical Nitrogen Reduction to Ammonia.

Ammonia (NH3) plays a significant role in the manufacture of fertilizers, nitrogen-containing chemical production, and hydrogen storage. The electrochemical nitrogen reduction reaction (e-NRR) is an attractive prospect for achieving clean and sustainable NH3 production, under mild conditions driven by renewable energy. The sluggish cleavage of N≡N bonds and poor selectivity of e-NRR are the primary challenges for e-NRR, over the competitive hydrogen evolution reaction (HER). The rational design of e-NRR electrocatalysts is of vital significance and should be based on a thorough understanding of the structure-activity relationship and mechanism. Among the various explored e-NRR catalysts, metal-based electrocatalysts have drawn increasing attention due to their remarkable performances. This review highlighted the recent progress and developments in metal-based electrocatalysts for e-NRR. Different kinds of metal-based electrocatalysts used in NH3 synthesis (including noble-metal-based catalysts, non-noble-metal-based catalysts, and metal compound catalysts) were introduced. The theoretical screening and the experimental practice of rational metal-based electrocatalyst design with different strategies were systematically summarized. Additionally, the structure-function relationship to improve the NH3 yield was evaluated. Finally, current challenges and perspectives of this burgeoning area were provided. The objective of this review is to provide a comprehensive understanding of metal-based e-NRR electrocatalysts with a focus on enhancing their efficiency in the future.

Balancing Volmer Step by Superhydrophilic Dual-Active Domains for Enhanced Hydrogen Evolution.

The reaction kinetics of hydrogen evolution reaction (HER) is largely determined by balancing the Volmer step in alkaline media. Bifunctionality as a proposed strategy can divide the work of water dissociation and intermediates (OH* and H*) adsorption/desorption. However, sluggish OH* desorption plagues water re-adsorption, which leads to poisoning effects of active sites. Some active sites may even directly act as spectators and do not participate in the reaction. Furthermore, the activity comparison under approximate nanostructure between bifunctional effect and single-exposed active sites is not fully understood. Here, a facile three-step strategy is adopted to successfully grow molybdenum disulfide (MoS2 ) on cobalt-containing nitrogen-doped carbon nanotubes (Co-NCNTs), forming obvious dual active domains. The active sites on domains of Co-NCNTs and MoS2  and the tuned electronic structure at the heterointerface trigger the bifunctional effect to balance the Volmer step and improve the catalytic activity. The HER driven by the bifunctional effect can significantly optimize the Gibbs free energy of water dissociation and hydrogen adsorption, resulting in fast reaction kinetics and superior catalytic performance. As a result, the Co-NCNTs/MoS2  catalyst outperforms other HER electrocatalysts with low overpotential (58 and 84 mV at 10 mA cm-2  in alkaline and neutral conditions, respectively), exceptional stability, and negligible degradation.

Improving Relative Permittivity and Suppressing Dielectric Loss of Triboelectric Layers for High-Performance Wearable Electricity Generation.

High relative permittivity and low dielectric loss are two desired parameters of a triboelectric layer to enhance its mechanical-to-electrical energy conversion efficiency in a triboelectric nanogenerator (TENG). However, the elevated permittivity of the triboelectric layer is always accompanied by increasing dielectric loss, limiting further improvement or even reducing the electrical output. Herein, we report a method for improving the relative permittivity and suppressing the dielectric loss of the triboelectric layer via nanoscale design at the particle-polymer interface. When incorporated with 2 wt % Ag@C, the triboelectric-layer-enhanced TENG (TLE-TENG) presents a 2.6-fold increment in relative permittivity and a 302% current enhancement. An instantaneous peak power density of 1.22 W m-2, an excellent pressure sensitivity of 90.95 V kPa-1, and an optimized sheet resistance (∼0.14 Ω/sq) are attributes of this greatly enhanced device. Such improvements bode well for the implementation of these enhancing strategies to help position TLE-TENGs as pervasive and sustainable power sources and active self-powered sensors in the era of the Internet of Things.

Self-charging electrostatic face masks leveraging triboelectrification for prolonged air filtration.

Electrostatic adsorption is an important complement to the mechanical filtration for high-efficiency air filtering. However, the electrostatic charge decays with time, especially in humid conditions. In this work, a self-charging air filter is presented to capture airborne particles in an efficient and long-lasting manner without the need of external power sources. Leveraging the triboelectric effect between the electrospun poly(vinylidene fluoride) nanofiber film and nylon fabric, the self-charging air filter-based mask excited by breathing can continuously replenish electrostatic charges. As a result, its effective lifespan is up to 60 hours (including 30 hours of wearing), with a minimum filtration efficiency of 95.8% for 0.3-µm particles. The filtration efficiency and lifespan are significantly higher than those of a commercial surgical mask. Furthermore, we uncover the quantitative relation between filtration efficiency and surface electrostatic potential. This work provides an effective strategy to significantly prolong the electrostatic adsorption efficacy for high-performance air-filtering masks.

Photocatalytic Oxidation for Volatile Organic Compounds Elimination: From Fundamental Research to Practical Applications.

Photocatalysis is regarded as one of the most promising technologies for indoor volatile organic compounds (VOCs) elimination due to its low cost, safe operation, energy efficiency, and high mineralization efficiency under ambient conditions. However, the practical applications of this technology are limited, despite considerable research efforts in recent decades. Until now, most of the works were carried out in the laboratory and focused on exploring new catalytic materials. Only a few works involved the immobilization of catalysts and the design of reactors for practical applications. Therefore, this review systematically summarizes the research and development on photocatalytic oxidation (PCO) of VOCs, with emphasis on recent catalyst's immobilization and reactor designs in detail. First, different types of photocatalytic materials and the mechanisms for PCO of VOCs are briefly discussed. Then, both the catalyst's immobilization techniques and reactor designs are reviewed in detail. Finally, the existing challenges and future perspectives for PCO of VOCs are proposed. This work aims to provide updated information and research inspirations for the commercialization of this technology in the future.

Engineering Single-Atom Active Sites on Covalent Organic Frameworks for Boosting CO2 Photoreduction.

Solar carbon dioxide (CO2) conversion is an emerging solution to meet the challenges of sustainable energy systems and environmental/climate concerns. However, the construction of isolated active sites not only influences catalytic activity but also limits the understanding of the structure-catalyst relationship of CO2 reduction. Herein, we develop a universal synthetic protocol to fabricate different single-atom metal sites (e.g., Fe, Co, Ni, Zn, Cu, Mn, and Ru) anchored on the triazine-based covalent organic framework (SAS/Tr-COF) backbone with the bridging structure of metal-nitrogen-chlorine for high-performance catalytic CO2 reduction. Remarkably, the as-synthesized Fe SAS/Tr-COF as a representative catalyst achieved an impressive CO generation rate as high as 980.3 µmol g-1 h-1 and a selectivity of 96.4%, over approximately 26 times higher than that of the pristine Tr-COF under visible light irradiation. From X-ray absorption fine structure analysis and density functional theory calculations, the superior photocatalytic performance is attributed to the synergic effect of atomically dispersed metal sites and Tr-COF host, decreasing the reaction energy barriers for the formation of *COOH intermediates and promoting CO2 adsorption and activation as well as CO desorption. This work not only affords rational design of state-of-the-art catalysts at the molecular level but also provides in-depth insights for efficient CO2 conversion.

Valence Engineering of Polyvalent Cobalt Encapsulated in a Carbon Nanofiber as an Efficient Trifunctional Electrocatalyst for the Zn-Air Battery and Overall Water Splitting.

The rapid development of electrochemical power systems has prompted high demand for nonprecious trifunctional electrocatalysts with superior performance, prolonged stability, and low cost for oxygen reduction reaction (ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER). Here, a valence engineering strategy is devised to construct a morphology with polyvalent cobalt encapsulated in nitrogen-doped carbon nanofibers (Co/N-CNFs). The diverse cobalt valence states of the Co/N-CNF catalysts contribute to their excellent catalytic effect and high durability in multiple electrochemical processes. The optimal Co/N-CNF catalyst fabricated exhibits a high half-wave potential of ORR (0.86 V) and low overpotentials of OER (380 mV) and HER (241 mV) at 10 mA cm-2. The Co/N-CNF-based Zn-air battery possesses a high charge-discharge efficiency as well as a good cycle stability (50 h at 10 mA cm-2 and 120 h at 20 mA cm-2), much superior to the Pt/C-based batteries. Furthermore, the Co/N-CNF catalyst could perform efficient overall water splitting.

Atomically Dispersed Iron Metal Site in a Porphyrin-Based Metal-Organic Framework for Photocatalytic Nitrogen Fixation.

The rational design of photocatalysts for efficient nitrogen (N2) fixation at ambient conditions is important for revolutionizing ammonia production and quite challenging because the great difficulty lies in the adsorption and activation of the inert N2. Inspired by a biological molecule, chlorophyll, featuring a porphyrin structure as the photosensitizer and enzyme nitrogenase featuring an iron (Fe) atom as a favorable binding site for N2via π-backbonding, here we developed a porphyrin-based metal-organic framework (PMOF) with Fe as the active center as an artificial photocatalyst for N2 reduction reaction (NRR) under ambient conditions. The PMOF features aluminum (Al) as metal node imparting high stability and Fe incorporated and atomically dispersed by residing at each porphyrin ring promoting the adsorption and the activation of N2, termed Al-PMOF(Fe). Compared with the pristine Al-PMOF, Al-PMOF(Fe) exhibits a substantial enhancement in NH3 yield (635 µg g-1cat.) and production rate (127 µg h-1 g-1cat.) of 82% and 50%, respectively, on par with the best-performing MOF-based NRR catalysts. Three cycles of photocatalytic NRR experimental results corroborate a stable photocatalytic activity of Al-PMOF(Fe). The combined experimental and theoretical results reveal that the Fe-N site in Al-PMOF(Fe) is the active photocatalytic center that can mitigate the difficulty of the rate-determining step in photocatalytic NRR. The possible reaction pathways of NRR on Al-PMOF(Fe) were established. Our study of porphyrin-based MOF for the photocatalytic NRR will provide insight into the rational design of catalysts for artificial photosynthesis.

Coalescence-Induced Jumping Droplets on Nanostructured Biphilic Surfaces with Contact Electrification Effects.

Benefitting from the coalescence-induced droplet jumping on superhydrophobic surfaces, the condensing droplets on heat exchangers can be removed efficiently, significantly improving the condensation heat-transfer performance of various thermal applications. However, the enhancement of droplet jumping height and self-removal to further improve the condensation heat-transfer performance of the thermal applications remains a challenge due to considerable interfacial adhesion caused by the inevitable partial-Wenzel state condensing droplets on superhydrophobic surfaces. In this study, a biphilic nanostructure is developed to effectively improve the droplet jumping height by decreasing the interfacial adhesion with the formation of Cassie-like droplets. Under atmospheric conditions, ∼28% improvement of droplet jumping height is achieved on a biphilic surface compared to that of a superhydrophobic surface. Additionally, the droplet contact electrification on biphilic surfaces discovered in this work allows the droplets to jump ∼137% higher compared with that under atmospheric conditions. Furthermore, the droplet jumping and electrification mechanisms on the biphilic surface are revealed by building a theoretical model that can predict the experimental results well. Apart from being a milestone for the droplet jumping physics development on biphilic nanostructures, this work also provides new insights into the micro-droplet discipline.

Dynamic Activation of Adsorbed Intermediates via Axial Traction for the Promoted Electrochemical CO2 Reduction.

Regulating the local environment and structure of metal center coordinated by nitrogen ligands (M-N4 ) to accelerate overall reaction dynamics of the electrochemical CO2 reduction reaction (CO2 RR) has attracted extensive attention. Herein, we develop an axial traction strategy to optimize the electronic structure of the M-N4 moiety and construct atomically dispersed nickel sites coordinated with four nitrogen atoms and one axial oxygen atom, which are embedded within the carbon matrix (Ni-N4 -O/C). The Ni-N4 -O/C electrocatalyst exhibited excellent CO2 RR performance with a maximum CO Faradic efficiency (FE) close to 100 % at -0.9 V. The CO FE could be maintained above 90 % in a wide range of potential window from -0.5 to -1.1 V. The superior CO2 RR activity is due to the Ni-N4 -O active moiety composed of a Ni-N4 site with an additional oxygen atom that induces an axial traction effect.

Interface Modulation of MoS2 /Metal Oxide Heterostructures for Efficient Hydrogen Evolution Electrocatalysis.

Developing efficient earth-abundant MoS2 based hydrogen evolution reaction (HER) electrocatalysts is important but challenging due to the sluggish kinetics in alkaline media. Herein, a strategy to fabricate a high-performance MoS2 based HER electrocatalyst by modulating interface electronic structure via metal oxides is developed. All the heterostructure catalysts present significant improvement of HER electrocatalytic activities, demonstrating a positive role of metal oxides decoration in promoting the rate-limited water dissociation step for the HER mechanism in alkaline media. The as-obtained MoS2 /Ni2 O3 H catalyst exhibits a low overpotential of 84 mV at 10 mA cm-2 and small charge-transfer resistance of 1.5 Ω in 1 m KOH solution. The current density (217 mA cm-2 ) at the overpotential of 200 mV is about 2 and 24 times higher than that of commercial Pt/C and bare MoS2 , respectively. Additionally, these MoS2 /metal oxides heterostructure catalysts show outstanding long-term stability under a harsh chronopotentiometry test. Theoretical calculations reveal the varied sensitivity of 3d-band in different transition oxides, in which Ni-3d of Ni2 O3 H is evidently activated to achieve fast electron transfer for HER as the electron-depletion center. Both electronic properties and energetic reaction trends confirm the high electroactivity of MoS2 /Ni2 O3 H in the adsorption and dissociation of H2 O for highly efficient HER in alkaline media.

Designing bifuncitonal molecular devices with a metalloporphyrin dimer.

Many organic molecules have unique magnetic properties and can potentially serve as excellent molecular spin devices, which is worth exploring deeply. Here, the spin transport properties of Mn, Fe, Co and Cu porphyrin dimer devices are investigated based on the first principles method. The spin filtering efficiencies of these molecular devices are maintained at 100% within certain applied voltage ranges and magnetoresistance ratios are higher than 108% which increase as the voltage increases. To explain the excellent spin-filtering and giant magnetoresistance effects, analysis of spin electron densities and transmission spectra indicates that magnetic properties are mainly contributed by the metal atoms and their neighbouring N atoms. From the transmission pathway studies, spin electrons come mainly through the π-conjugated structure of the metal porphyrin ring. Interestingly, in the Cu porphyrin dimer device, magnetic moments of the Cu-N structure in the Cu porphyrin dimer device show spin behaviors different from those of Mn, Fe and Co porphyrin dimer devices.

Boosting Oxygen Reduction of Single Iron Active Sites via Geometric and Electronic Engineering: Nitrogen and Phosphorus Dual Coordination.

Atomically dispersed transition metal active sites have emerged as one of the most important fields of study because they display promising performance in catalysis and have the potential to serve as ideal models for fundamental understanding. However, both the preparation and determination of such active sites remain a challenge. The structural engineering of carbon- and nitrogen-coordinated metal sites (M-N-C, M = Fe, Co, Ni, Mn, Cu, etc.) via employing new heteroatoms, e.g., P and S, remains challenging. In this study, carbon nanosheets embedded with nitrogen and phosphorus dual-coordinated iron active sites (denoted as Fe-N/P-C) were developed and determined using cutting edge techniques. Both experimental and theoretical results suggested that the N and P dual-coordinated iron sites were favorable for oxygen intermediate adsorption/desorption, resulting in accelerated reaction kinetics and promising catalytic oxygen reduction activity. This work not only provides efficient way to prepare well-defined single-atom active sites to boost catalytic performance but also paves the way to identify the dual-coordinated single metal atom sites.

Effect of composites based nickel foam anode in microbial fuel cell using Acetobacter aceti and Gluconobacter roseus as a biocatalysts.

This study explores the use of materials such as chitosan (chit), polyaniline (PANI) and titanium carbide (TC) as anode materials for microbial fuel cells. Nickel foam (NF) was used as the base anode substrate. Four different types of anodes (NF, NF/PANI, NF/PANI/TC, NF/PANI/TC/Chit) are thus prepared and used in batch type microbial fuel cells operated with a mixed consortium of Acetobacter aceti and Gluconobacter roseus as the biocatalysts and bad wine as a feedstock. A maximum power density of 18.8Wm(-3) (≈2.3 times higher than NF) was obtained in the case of the anode modified with a composite of PANI/TC/Chit. The MFCs running under a constant external resistance of (50Ω) yielded 14.7% coulombic efficiency with a maximum chemical oxygen demand (COD) removal of 87-93%. The overall results suggest that the catalytic materials embedded in the chitosan matrix show the best performance and have potentials for further development.

Recent Development of Plasmonic Resonance-Based Photocatalysis and Photovoltaics for Solar Utilization.

Increasing utilization of solar energy is an effective strategy to tackle our energy and energy-related environmental issues. Both solar photocatalysis (PC) and solar photovoltaics (PV) have high potential to develop technologies of many practical applications. Substantial research efforts are devoted to enhancing visible light activation of the photoelectrocatalytic reactions by various modifications of nanostructured semiconductors. This review paper emphasizes the recent advancement in material modifications by means of the promising localized surface plasmonic resonance (LSPR) mechanisms. The principles of LSPR and its effects on the photonic efficiency of PV and PC are discussed here. Many research findings reveal the promise of Au and Ag plasmonic nanoparticles (NPs). Continual investigation for increasing the stability of the plasmonic NPs will be fruitful.

Facile synthesis of nitrogen and sulfur codoped carbon from ionic liquid as metal-free catalyst for oxygen reduction reaction.

Developing metal-free catalysts for oxygen reduction reaction (ORR) is a great challenge in the development of fuel cells. Nitrogen and sulfur codoped carbon with remarkably high nitrogen content up to 13.00 at % was successfully fabricated by pyrolysis of homogeneous mixture of exfoliated graphitic flakes and ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide ([Bimi][Tf2N]). The exfoliated graphite flakes served as a structure-directing substance as well as additional carbon source in the fabrication. It was demonstrated that the use of graphite flakes increased the nitrogen doping level, optimized the composition of active nitrogen configurations, and enlarged the specific surface area of the catalysts. Electrochemical characterizations revealed that the N and S codoped carbon fabricated by this method exhibited superior catalytic activities toward ORR under both acidic and alkaline conditions. Particularly in alkaline solution, the current catalyst compared favorably to the conventional 20 wt % Pt/C catalyst via four-electron transfer pathway with better ORR selectivity. The excellent catalytic activity was mainly ascribed to high nitrogen doping content, appropriate constitution of active nitrogen configurations, large specific surface area, and synergistic effect of N and S codoping.

Ultrafine single-crystal TiOF2 nanocubes with mesoporous structure, high activity and durability in visible light driven photocatalysis.

Single crystal TiOF2 nanocubes assembled into a mesoporous structure were synthesized by alcoholysis of TiF4 under solvothermal conditions, which displayed spectral response in the visible area owing to the intrinsic narrow energy band gap. Mechanism studies revealed that TiOF2 was formed via consecutive hydrolysis reactions and the H2O produced by condensation between two alcohols played a key role in determining the TiOF2 crystal growth and its transformation to anatase TiO2. The TiOF2 nanocube size could be easily adjusted by changing either alcoholysis time, or solvothermal temperature, or alcohol kind owing to the different H2O production rate and amount. The small-sized TiOF2 nanocubes with large surface area exhibited high activity in photocatalytic degradation of Rhodamine B (RhB) and 4-chlorophenol (4-CP) owing to the enhanced adsorption for reactant molecules and the reduced photoelectron-hole recombination rate. Meanwhile, they also showed strong durability since the mesoporous structure enhanced the stability against either the phase transformation from TiOF2 crystal to anatase TiO2 or the agglomeration of TiOF2 nanocubes.