Brønsted-acid sites induced photocatalytic cracking of low-polarity polyethylene plastics

Polyolefins such as polyethylene(PE)are one of the largest-scale synthetic plastics and play a key role in modern society.However,polyethylene is extremely inert to chemical recycling owing to its lack of chemical functionality and low polarity,making it one of the most challenging environmental hazards globally.Herein,we developed a phosphorylated CeO_(2)catalyst by an organophosphate precursor and featured efficient photocatalysis of low-density polyethylene(LDPE)without the acid or alkaline pre-treatment.Compared to pristine CeO_(2),the surface phosphorylation allows to introduce Brønsted acid sites,which facilitate to form carbonium ions on LDPE via protonation.In addition,the suitable band structure of the phosphorylated CeO_(2)catalyst enables efficient photoabsorption and generates reactive oxygen species,leading to the C–C bond cleavage of LDPE.As a result,the phosphorylated CeO_(2)catalyst exhibited an outstanding carbon conversion rate of>94%after 48 h of photocatalysis under 50 mW/cm^(2)of simulated sunlight,with a high CO_(2)product selectivity of>99%.Furthermore,the PE microparticles with sizes larger than 10μm released from LDPE plastic wrap were directly and completely degraded by photocatalysis within 12 h,suggesting an attractive and environmentally benign strategy of utilizing solar energy-based photocatalysis for reducing potential hazards of LDPE plastic trashes.

Few‐layer carbon nitride photocatalysts for solar fuels and chemicals:Current status and prospects

Converting sunlight directly to fuels and chemicals is a great latent capacity for storing renewable energy.Due to the advantages of large surface area,short diffusion paths for electrons,and more exposed active sites,few‐layer carbon nitride(FLCN)materials present great potential for production of solar fuels and chemicals and set off a new wave of research in the last few years.Herein,the recent progress in synthesis and regulation of FLCN‐based photocatalysts,and their applications in the conversion of sunlight into fuels and chemicals,is summarized.More importantly,the regulation strategies from chemical modification to microstructure control toward the production of solar fuels and chemicals has been deeply analyzed,aiming to inspire critical thinking about the effective approaches for photocatalyst modification rather than developing new materials.At the end,the key scientific challenges and some future trend of FLCN‐based materials as advanced photocatalysts are also discussed.

Electrochemical conversion of C1 molecules to sustainable fuels in solid oxide electrolysis cells

Stimulated by increasing environmental awareness and renewable-energy utilization capabilities,fuel cell and electrolyzer technologies have emerged to play a unique role in energy storage,conversion,and utilization.In particular,solid oxide electrolysis cells(SOECs)are increasingly attracting the interest of researchers as a platform for the electrolysis and conversion of C1 molecules,such as carbon dioxide and methane.Compared to traditional catalysis methods,SOEC technology offers two major advantages:high energy efficiency and poisoning resistance,ensuring the long-term robustness of C1-to-fuels conversion.In this review,we focus on state-of-the-art technologies and introduce representative works on SOEC-based techniques for C1 molecule electrochemical conversion developed over the past several years,which can serve as a timely reference for designing suitable catalysts and cell processes for efficient and practical conversion of C1 molecules.The challenges and prospects are also discussed to suggest possible research directions for sustainable fuel production from C1 molecules by SOECs in the near future.

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.

Copper‐doped nickel oxyhydroxide for efficient electrocatalytic ethanol oxidation

Rational design of low‐cost and efficient electrocatalysts for ethanol oxidation reaction(EOR)is imperative for electrocatalytic ethanol fuel cells.In this work,we developed a copper‐doped nickel oxyhydroxide(Cu‐doped NiOOH)catalyst via in situ electrochemical reconstruction of a NiCu alloy.The introduction of Cu dopants increases the specific surface area and more defect sites,as well as forms high‐valence Ni sites.The Cu‐doped NiOOH electrocatalyst exhibited an excellent EOR performance with a peak current density of 227 mA·cm^(–2)at 1.72 V versus reversible hydrogen electrode,high Faradic efficiencies for acetate production(>98%),and excellent electrochemical stability.Our work suggests an attractive route of designing non‐noble metal based electrocatalysts for ethanol oxidation.

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.

Enhanced N-doping in mesoporous carbon for efficient electrocatalytic CO2 conversion

The capability of electrocatalytic reducti on of carbon dioxide(CO2)using nitrogen(N)-doped carb on strongly depe nds on the N-dopi ng level and their types.In this work,we developed a strategy to generate mesoporous N-doped carb on frameworks with tun able configurati ons and contents of N dopants,by using a secondary doping process via the treatment of N,N-dimethylformamide(DMF)solvent.The obtained mesoporous N-doped carbon(denoted as MNC-D)served as an efficient electrocatalyst for electroreduction of CO2 to CO.A high Faradaic efficiency of^92%and a partial current density for CO of-6.8 mA·cm^-2 were achieved at a potential of-0.58 V vs.RHE.Electrochemical analyses further revealed that the active sites within the N-doped carb on catalysts were the pyridinic N and defects gen erated by the DMF treatme nt,which enhan ced the activati on and adsorpti on CO2 molecules.Our study suggests a new approach to develop efficie nt carb on-based catalysts for potential scalable CO2 reduction reaction(CO2RR)to fuels and chemicals.

Aqueous electrocatalytic N2 reduction under ambient conditions

Recently, the electrochemical N2 reduction reaction （NRR） in aqueous electrolytes at ambient temperature and pressure has demonstrated its unique advantages and potentials. The reactants are directly derived from gaseous N2 and water, which are naturally abundant, and NH3 production is important for fertilizers and other industrial applications. To improve the conversion yield and selectivity （mainly competing with water reduction）, electrocatalysts must be rationally designed to optimize the mass transport, chemisorption, and transduction pathways of protons and electrons. In this review, we summarize recent progress in the electrochemical NRR. Studies of electrocatalyst designs are summarized for different categories, including metal-based catalysts, metal oxide-derived catalysts, and hybrid catalysts. Strategies for enhancing the NRR performance based on the facet orientation, metal oxide interface, crystallinity, and nitrogen vacancies are presented. Additional system designs, such as lithium-nitrogen batteries, and the solvent effect are introduced. Finally, existing challenges and prospects are discussed.

Pushing the activity of CO2 electroreduction by system engineering

As a promising technology that may solve global environmental challenges and enable intermittent renewable energy storage as well as zero-carbon-emission energy cycling, the carbon dioxide reduction reaction has been extensively studied in the past several years. Beyond the fruitful progresses and innovations in catalysts, the system engineering-based research on the full carbon dioxide reduction reaction is urgently needed toward the industrial application. In this review, we summarize and discuss recent works on the innovations in the reactor architectures and optimizations based on system engineering in carbon dioxide reduction reaction. Some challenges and future trends in this field are further discussed, especially on the system engineering factors.

Atomic layer deposition-induced integration of N-doped carbon particles on carbon foam for flexible supercapacitor

Flexible devices have attracted abundant attention in energy storage systems.In this paper,we presented a novel approach for fabricating flexible supercapacitor based on metal organic frameworks-derived material.In this approach,a uniform zeolitic imidazolate frameworks-8 layer with a high mass loading was deposited on a flexible carbon foam(CF)skeleton efficiently by the induction of a uniform ZnO nanomembrane prepared via an atomic layer deposition technique.A flexible N-doped carbon particle-carbon foam(N-CP-CF)composite with a hierarchically porous structure and a large specific surface area(i.e.,538 m^(2) g^(-1))was obtained in a subsequent pyrolysis process.The resultant materials have the excellent electrochemical performance(i.e.,a high specific capacitance of 300 F g^(-1) and a high energy density of 20.8 W h kg^(-1)).The N-CP-CF composite can provide a stable capacitance(i.e.,250 F g^(-1))and an energy density(i.e.,17.36 W h kg^(-1))under large deformation(25% of original thickness).This work could propose a promising strategy in fabrication of flexible electrode with a large potential towards energy storage applications in the future.

2020 Roadmap on gas-involved photo-and electro-catalysis

Green reactions not only provide us chemical products without any pollution,but also offer us the viable technology to realize difficult tasks in normal conditions.Photo-,photoelectro-,and electrocatalytic reactions are indeed powerful tools to help us to embrace bright future.Especially,some gas-involved reactions are extremely useful to change our life environments from energy systems to liquid fuels and cost-effective products,such as H2 evolution(H2 production),02 evolution/reduction,CO2 reduction,N2 reduction(or N2 fixation) reactions.We can provide fuel cells clean H2 for electric vehicles from H2 evolution reaction(HER),at the same time,we also need highly efficient 02 reduction reaction(ORR) in fuel cells for improving the reaction kinetics.Moreover,we can get the clean oxidant O2 from water through O2 evolution reaction(OER),and carry out some reactions without posing any pollution to reaction systems.Furthermore,we can translate the greenhouse gas CO2 into useful liquid fuels through CO2 reduction reaction(CRR).Last but not the least,we can get ammonia from N2 reduction reaction(NRR),which can decrease energy input compared to the traditional Hubble process.These reactions,such as HER,ORR,OER,CRR and NRR could be realized through solar-,photoelectro-and electro-assisted ways.For them,the catalysts used play crucial roles in determining the efficiency and kinds of products,so we should consider the efficiency of catalysts.However,the cost,synthetic methods of catalysts should also be considered.Nowadays,significant progress has been achieved,however,many challenges still exist,reaction systems,catalysts underlying mechanisms,and so on.As extremely active fields,we should pay attention to them.Under the background,it has motivated us to contribute with a roadmap on ’GasInvolved Photo-and Electro-Catalysis’.

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.

Tuning Structures and Microenvironments of Cu-Based Catalysts for Sustainable CO_(2) and CO Electroreduction

CONSPECTUS:The carbon balance has been disrupted by the widespread use of fossil fuels and subsequent excessive emissions of carbon dioxide(CO_(2)),which has become an increasingly critical environmental challenge for human society.The production and use of renewable energy sources and/or chemicals have been proposed as important strategies to reduce emissions,of which the electrochemical CO_(2)(or CO)reduction reaction(CO_(2)RR/CORR)in the aqueous systems represents a promising approach.Benefitted by the capacity of manufacturing high-value-added products(e.g.,ethylene,ethanol,formic acid,etc.)with a net-zero carbon emission,copper-based CO_(2)RR/CORR powered by sustainable electricity is regarded as a potential candidate for carbon neutrality.However,the diversity of selectivities in copper-based systems poses a great challenge to the research in this field and sets a great obstacle for future industrialization.To date,scientists have revealed that the electrocatalyst design and preparation play a significant role in achieving efficient and selective CO_(2)-to-chemical(or CO-to-chemical)conversion.Although substantial efforts have been dedicated to the catalyst preparation and corresponding electrosynthesis of sustainable chemicals from CO_(2)/CO so far,most of them are still derived from empirical or random searches,which are relatively inefficient and cost-intensive.Most of the mechanism studies have suggested that both intrinsic properties(such as electron states)and extrinsic environmental factors(such as surface energy)of a catalyst can significantly alter catalytic performance.Thus,these two topics are mainly discussed for copper-based catalyst developments in this Account.Here,we provided a concise and comprehensive introduction to the well-established strategies employed for the design of copperbased electrocatalysts for CO_(2)RR/CORR.We used several examples from our research group,as well as representative studies of other research groups in this field during the recent five years,with the perspectives of tuning local electron states,regulating alloy phases,modifying interfacial coverages,and adjusting other interfacial microenvironments(e.g.,molecule modification or surface energy).Finally,we employed the techno-economic assessment with a viewpoint on the future application of CO_(2)/CO electroreduction in manufacturing sustainable chemicals.Our study indicates that when carbon price is taken into account,the electrocatalytic CO_(2)-to-chemical conversion can be more market-competitive,and several potential value-added products including formate,methanol,ethylene,and ethanol can all make profits under optimal operating conditions.Moreover,a downstream module employing traditional chemical industrial processes(e.g.,thermal polymerization,catalytic hydrolysis,or condensation process)will also make the whole electrolysis system profitable in the future.These design principles,combined with the recent advances in the development of efficient copper-based electrocatalysts,may provide a low-cost and long-lasting catalytic system for a profitable industrial-scale CO_(2)RR in the future.

Atomically-dispersed catalyst by solid-liquid phase transition for CO_(2)electroreduction

The electrochemical reduction of carbon dioxide(CO_(2))to value-added fuels and chemicals provides a promising way to realize sustainable carbon recycling[1].Developing robust electrocatalysts with high activity and selectivity is critically important for efficient electrochemical CO_(2)reduction reaction(CO_(2)RR).Generally,it is challenging to achieve high efficiency and selectivity simultaneously in the CO_(2)RR due to the multi-proton/electron transfer processes and complex reaction intermediates.