Photoelectrochemical seawater oxidation with metal oxide materials:Challenges and opportunities

Photocatalytic water oxidation is a crucial counter-electrode reaction in the process of photoelectrochemical energy conversion.Despite its importance,challenges remain in effectively and sustainably converting water to oxygen,particularly with readily available and inexpensive electrolyte solutions such as seawater.While metal oxide materials have demonstrated their advantages in promoting efficiency by reducing overpotential and improving light utilization,stability remains limited by corrosion in multicomponent seawater.In this paper,we reviewed the relationship between four basic concepts including photoelectrochemistry,metal oxide,water oxidation and seawater to better understand the challenges and opportunities in photoelectrochemical(PEC)seawater oxidation.To overcome these challenges,the advances in material design,interfacial modification,local environment control and reactor design have been further reviewed to benefit the industrial PEC seawater oxidation.Noticeably,we demonstrate engineered layered metal oxide electrodes and cell structures that enable powerful and stable seawater oxidation.We also outline and advise on the future direction in this area.

Electroreduction of air‐level CO_(2) with high conversion efficiency

The electrochemical conversion of carbon dioxide(CO_(2))has been attracting increasingly research interest in the past decade,with the ultimate goal of utilizing electricity from renewable energy to realize carbon neutrality,as well as economic and energy benefits.Nonetheless,the capture and concentrating of CO_(2) cost a substantial portion of energy,while almost all the reported researches showed CO_(2) electroreduction under high concentrations of(typically pure)CO_(2) reactants,and only very few recent studies have investigated the capability of applying low CO_(2) concentrations(such as~10%in flue gases).In this work,we first demonstrated the electroreduction of 0.03%CO_(2)(in helium)in a homemade gas‐phase electrochemical electrolyzer,using a low‐cost copper(Cu)or nanoscale copper(nano‐Cu)catalyst.Mixed with steam,the gas‐phase CO_(2) was directly delivered onto the gas‐solid interface with the Cu catalyst and reduced to CO,without the need/constraint of being adsorbed by aqueous solution or alkaline electrolytes.By tuning the catalyst and experi‐mental parameters,the conversion efficiency of CO_(2) reached as high as~95%.Furthermore,we demonstrated the direct electroreduction of 0.04%CO_(2) from real air sample with an optimized conversion efficiency of~79%,suggesting a promising perspective of the electroreduction ap‐proach toward direct CO_(2) conversion.

Efficient CO_(2) fixation with acetophenone on Ag-CeO_(2) electrocatalyst by a double activation strategy

The electrocarboxylation reaction is an attractive means to convert CO_(2) into valuable chemicals under ambient conditions,while it still suffers from low efficiency due to the high stability of CO_(2).In this work,we report a double activation strategy for simultaneously activating CO_(2) and acetophenone by silver-doped CeO_(2)(Ag-CeO_(2)) nanowires,featuring as an effective electrocatalyst for electrocarboxylation of acetophenone with CO_(2).Compared to the Ag foil,Ag nanoparticles and CeO_(2) nanowires,the Ag-CeO_(2)nanowire catalyst allowed to reduce the onset potential difference between CO_(2) and acetophenone activation,thus enabling efficient electrocarboxylation to form 2-phenyllactic acid.The Faradaic efficiency for producing 2-phenyllactic acid reached 91%at−1.8 V versus Ag/AgI.This double activation strategy of activating both CO_(2)and organic substrate molecules can benefit the catalyst design to improve activities and selectivities in upgrading CO_(2)fixation for higher-value electrocarboxylation.

Developing silicon-based photocathodes for CO_(2) conversion

Photoelectrochemical(PEC)conversion of CO_(2) presents a promising avenue for solar-driven chemical fuel production,with silicon emerging as a cost-effective and high-light-absorbing material pivotal to this technology.Aiming at exploring opportunities for industrializing PEC CO_(2) reduction(PEC-CO_(2)R)by minimizing reaction energy consumption,enhancing reaction efficiency and selectivity,this review summarizes recent advancements in developing Si-based photocathodes for PEC-CO_(2)R.It outlines the fundamental principles,advantages,and limitations of Si photocathodes with key performance metrics.Based on this understanding,the strategies to enhance the performance of the PEC-CO_(2)R system,including light absorption,charge separation,and catalytic reactions are categorized as the interfacial modification,active site decoration,and protective layer design.The design ideas of this advantageous three-layer structure in promoting the efficiency,stability,and selectivity have been clarified.Then,this review scrutinizes the influence of the photocathodic chemical environment.This review consolidates the mechanism insights and notable breakthroughs of various fuel generation processes within Si-based PEC-CO_(2)R systems.Providing this wealth of information offers an up-to-date perspective on the dynamic developments in silicon-based PEC-CO_(2) conversion and underscores the promising pathways toward the sustainable fuel synthesis from pollutant CO_(2).

MA Cation-Induced Diffusional Growth of Low-Bandgap FA-Cs Perovskites Driven by Natural Gradient Annealing

Low-bandgap formamidinium-cesium(FA-Cs)perovskites of FA_(1-x)CsxPbI_(3)(x<0:1)are promising candidates for efficient and robust perovskite solar cells,but their black-phase crystallization is very sensitive to annealing temperature.Unfortunately,the low heat conductivity of the glass substrate builds up a temperature gradient within from bottom to top and makes the initial annealing temperature of the perovskite film lower than the black-phase crystallization point(~150℃).Herein,we take advantage of such temperature gradient for the diffusional growth of high-quality FA-Cs perovskites by introducing a thermally unstable MA^(+)cation,which would firstly formα-phase FA-MA-Cs mixed perovskites with low formation energy at the hot bottom of the perovskite films in the early annealing stage.The natural gradient annealing temperature and the thermally unstable MA^(+)cation then lead to the bottom-to-top diffusional growth of highly orientatedα-phase FA-Cs perovskite,which exhibits 10-fold of enhanced crystallinity and reduced trap density(~3:85×10^(15) cm^(−3)).Eventually,such FA-Cs perovskite films were fabricated into stable solar cell devices with champion efficiency up to 23.11%,among the highest efficiency of MA-free perovskite solar cells.

Unraveling and tuning the linear correlation between CH_(4) and C_(2) production rates in CO_(2) electroreduction

Although many catalysts have been reported for the CO_(2)electroreduction to C_(1)or C_(2)chemicals,the insufficient understanding of fundamental correlations among different products still hinders the development of universal catalyst design strategies.Herein,we first discover that the surface*CO coverage is stable over a wide potential range and reveal a linear correlation between the partial current densities of CH_(4)and C_(2)products in this potential range,also supported by the theoretical kinetic analysis.Based on the mechanism that*CHO is the common intermediate in the formation of both CH_(4)(*CHO→CH4)and C_(1)(*CHO+*CO→C_(2)),we then unravel that this linear correlation is universal and the slope can be varied by tuning the surface*H or*CO coverage to promote the selectivity of CH_(4)or C_(2)products,respectively.As proofs-of-concept,using carbon-coated Cu particles,the surface*H coverage can be increased to enhance CH_(4)production,presenting a high CO_(2)-to-CH_(4)Faradaic efficiency(FE_(CH_(4))~52%)and an outstanding CH_(4)partial current density of-337 m A cm;.On the other hand,using an Agdoped Cu catalyst,the CO_(2)RR selectivity is switched to the C_(2)pathway,with a substantially promoted FE;of 79%and a high partial current density of-421 m A cm;.Our discovery of tuning intermediate coverages suggests a powerful catalyst design strategy for different CO_(2)electroreduction pathways.

Photodeposited FeOOH vs electrodeposited Co-Pi to enhance nanoporous BiVO4 for photoelectrochemical water splitting

Co-Pi and FeOOH cocatalysts were in-situ deposited on the surface of nanoporous BiVO4 photoelectrodes.The FeOOH cocatalyst has little effect on the BiVO4 samples＇ morphologies,while the electrodeposited CoPi cocatalyst seems to affect the surface of BiVO4 The impedance intensity modulated photocurrent spectroscopy（IMPS）,Mott-Schottky（M-S） techniques characterize BiVO4 samples photoelectrochemical performance with the deposition of Co-Pi and FeOOH.The Co-Pi/BiVO4 shows better photoelectrochemical performance than the FeOOH/BiVO4,but the FeOOH/BiVO4 exhibited the better stabilities.The flat band potential and slope of M-S plotof FeOOH/BiVO4 have little variations compared with BiVO4.In contrast,Co-Pi/BiVO4 exhibited the down shifted flat band potential,which is beneficial for the photoelectrochemical water oxidation.The electron transfer measurements revealed that the deposition of FeOOH and Co-Pi onto BiVO4 significantly enhanced the photoelectrochemical performance via reducing the interface resistance and promoting the electron transport.Furthermore,Co-Pi cocatalysts can further pin the transport-limiting traps and significantly facilitate the electron transport.

Solution chemistry quasi-epitaxial growth of atomic CaTiO_(3)perovskite layers to stabilize and passivate TiO_(2)photoelectrodes for efficient water splitting

Perovskite oxides with unique crystal structures and high defect tolerance are promising as atomic surface passivation layers for photoelectrodes for efficient and stable water splitting.However,controllably depositing and crystalizing perovskite-type metal oxides at the atomic level remains challenging,as they usually crystalize at higher temperatures than regular metal oxides.Here,we report a mild solution chemistry approach for the quasi-epitaxial growth of an atomic CaTiO_(3)perovskite layer on rutile TiO_(2)nanorod arrays.The high-temperature crystallization of CaTiO_(3)perovskite is overcome by a sequential hydrothermal conversion of the atomic amorphous TiOx layer to CaTiO_(3)perovskite.The atomic quasi-epitaxial CaTiO_(3)layer passivated TiO_(2)nanorod arrays exhibit more efficient interface charge transfer and high photoelectrochemical performance for water splitting.Such a mild solution-based approach for the quasi-epitaxial growth of atomic metal oxide perovskite layers could be a promising strategy for both fabricating atomic perovskite layers and improving their photoelectrochemical properties.