In this context, both sire-fertility testing and semen purification can potentially be improved through the application of nanotechnology. The identification of biomarkers — for example, ligands of lectins from Arachis hypogaea and Lens culinaris , sperm proteins ubiquitin and post-acrosomal, WW domain-binding protein — and trials of nanoparticle-based technologies for fertility testing and the nanopurification of bull semen for commercial artificial insemination have been reported.
Nanotechnology may serve the purposes of vegetarians who are willing to eat high proteinous food without killing the animals, in the form of in-vitro meat, cultured meat, or laboratory-grown meat. In the quest to maintain nutritional quality while achieving the quantities needed to fill the stomachs of hungry people in the coming years, nanotechnology may be the modern weapon. The transportability of livestock products with freshness is a great concern that may be ameliorated by the use of nanoparticles in the form of flexible pouches, laminates, and edible coatings.
Furthermore, nanobiotic silver may increase anabolic activities. Gold nanoparticle-based diagnosis kits detect poultry suffering from influenza virus. Ply formulations were prepared by three facile routes: covalent attachment onto US Food and Drug Administration-approved silica nanoparticles SNPs ; incorporation of SNP-Ply conjugates into a thin poly hydroxyethyl methacrylate film; and affinity binding to edible crosslinked starch nanoparticles via construction of a maltose-binding protein fusion for the surface incorporation of the listeria bacteriophage endolysin Ply Aquaculture plays an important role in global food production.
Aquaculture is the farming of fish and seafood and is one of the fastest growing sectors of the animal food producing sector. Young carp and sturgeon exhibited a faster rate of growth upon iron nanoparticle feeding. Moreover, nanoselenium was found more effective than organic selenomethionine in increasing muscle selenium content. For fish health in aquaculture, nanotechnological applications include antibacterial surfaces in the aquaculture system, nanodelivery of veterinary products in fish food using porous nanostructures, and nanosensors for detecting pathogens in the water.
Nanomaterials have shown great potential in a wide range of environmental applications due to the extremely small particle size, large surface area, and high reactivity. Calcium—alginate polymer is an excellent choice as an entrapment medium as it is nontoxic and has little solubility in water.
The use of nanoscale zero-valent iron diameter 10—90 nm with an average value of 35 nm entrapped in calcium—alginate beads showed great promise for aqueous arsenic treatment.
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The effect was shown on Escherichia coli , Staphylococcus carnosus , Penicillium roqueforti , and Chlorella vulgaris. Filters made from 2 nm diameter aluminium oxide nanofibers NanoCeram can remove viruses, bacteria, and protozoan cysts from water. Nanoscale iron oxide particles are extremely effective at binding and removing arsenic from groundwater. Pretreatment of rare earth oxide nanoparticles with phosphate in a neutral pH environment prevented their biological transformation into urchin shaped structures and profibrogenic effects.
Nanocochleates, 50 nm cylindrical cigarlike nanoparticles, can be used to deliver nutrients such as vitamins, lycopene, and omega fatty acids more efficiently to cells, without affecting the color or taste of food. Nanoparticles have promise for improving protection of farmed fish against diseases caused by pathogens. Chitosan nanoparticles are promising carriers for an oral plasmid DNA vaccine. Scientists have found a way to grow and harvest gold from crop plants. Nanoparticles could be industrially harvested. The gold nanoparticles can be mechanically separated by dissolving the organic material plant tissue following harvest.
Researchers reported the uptake of silver by living alfalfa plants from a silver-rich solid medium and the subsequent formation of silver nanoparticles. In terms of global food and livestock production, the main aspects of nanotechnology are improved quality and nutritional value. In spite of potential benefits that nanotechnology offers in the agri-food sector food production, feed for livestock, food ingredients, packaging, and nanobased smart systems , little is known on safety aspects of the application of nanotechnologies in food production and the incorporation of nanoparticles in food.
Moreover, consumers still lack knowledge about nanotechnology. Risk-assessment procedures are not specific to agri-food nano-materials, resulting in uncertainty regarding the nature and extent of potential risks in most cases. Elevated cerium content was detected in plant tissues exposed to cerium oxide nanoparticles, suggesting that cerium oxide nanoparticles were taken up by tomato roots and translocated to shoots and edible tissues.
This study sheds light on the long-term impact of cerium oxide nanoparticles on plant health and its implications for our food safety and security. The regulation specifically requires assessment and approval of active nanomaterial biocidal ingredients. The environmental and societal implications of nanotechnology was assessed. Such definition could lead to existing nanomaterials not being labeled due to an exemption provided for food additives approved on a European Union list.
Many diverse opportunities for nanotechnology exist to play an important role in agriculture and food production as well as in livestock production. The potential uses and benefits of nanotechnology are enormous. Productivity enhancement through nanotechnology-driven precision farming and maximization of output and minimization of inputs through better monitoring and targeted action is desirable. Nanotechnology enables plants to use water, pesticides, and fertilizers more efficiently. Nanotechnology use may bring potential benefits to farmers through food production and to the food industry through development of innovative products through food processing, preservation, and packaging.
Even so, less effort is going into applications of nanotechnology in agri-food sectors. Further, existing efforts are more oriented to reduce the negative impact of agrochemical products in the environment and human health, rather than the utilization of nanotechnology applications to improve their properties for food and livestock production. Experts envision numerous nanoparticulate agroformulations with higher bioavailability and efficacy and better selectivity in the near future.
Multidisciplinary approaches could potentially improve food production, incorporating new emerging technologies and disciplines such as chemical biology integrated with nanotechnologies to tackle existing biological bottlenecks that currently limit further developments. The potential benefits of nanotechnology for agriculture, food, fisheries, and aquaculture need to be balanced against concerns for the soil, water, environment, and the occupational health of workers. National Center for Biotechnology Information , U. Journal List Nanotechnol Sci Appl v. Nanotechnol Sci Appl. Published online May Bhupinder Singh Sekhon.
Author information Copyright and License information Disclaimer. Non-commercial uses of the work are permitted without any further permission from Dove Medical Press Limited, provided the work is properly attributed. This article has been cited by other articles in PMC. Abstract Nanotechnology is one of the most important tools in modern agriculture, and agri-food nanotechnology is anticipated to become a driving economic force in the near future. Keywords: agriculture, food, nanotechnology, nanoparticle, nanopesticides, nanosensors, smart delivery systems. Video abstract Click here to view.
Open in a separate window. Figure 1. Nanotechnology and nanomaterials Nanoscale refers to size dimensions typically between approximately 1— nm or more appropriately, 0. Biological natural nanoparticles Biological naturally occurring nanoparticles nanoclay, tomato carotenoid lycopene, many chemicals derived from soil organic matter, lipoproteins, exosomes, magnetosomes, viruses, ferritin have diverse structures with wide-ranging biological roles. Nanoagrochemicals Pesticides are commonly used in agriculture to improve crop yield and efficiency.
Figure 2. Figure 3. Molecular structure of gelator all-trans tri p-phenylene vinylene bis-aldoxime. Nanofertilizers Nanofertilizer technology is very innovative, and scant reported literature is available in the scientific journals. Nanobiotechnology in agri-food production Nanobiotechnology opportunities include food, agriculture and energy applications. Nanotechnology and agri-environment The use of pesticides and fertilizers to improve food production leads to an uncontrolled release of undesired substances into the environment.
Nanotechnological applications in agrowaste reduction and high-value products such as biofuels Currently, the discouraging energy trends and challenges are a result of overreliance on limited fossil fuels tied with ever-increasing energy demand. Nanotechnology in hydroponics Hydroponics a branch of agriculture is the technology of growing plants without soil and is widely used around the globe for growing food crops.
Nanotechnology in organic agriculture An International Federation on Organic Agriculture Movements Position Paper on the Use of Nanotechnologies and Nanomaterials in Organic Agriculture rejected the use of nanotechnology in organic agriculture. Nanotechnology for crop improvement An enhanced production has been observed by foliar application of nanoparticles as fertilizer. Nanofiltration Nanotechnology has played a very important role in developing a number of low-energy alternatives, among which three are most promising: 1 protein—polymer biomimetic membranes; 2 aligned-carbon nanotube membranes; and 3 thin-film nanocomposite membranes.
Nanofoods The agri-food industries have been investing huge money into nanotechnology research. Nanotechnology for aquaculture and fisheries Aquaculture plays an important role in global food production. Particle farming Scientists have found a way to grow and harvest gold from crop plants. Toxicology aspects, associated risks, and regulatory aspects In terms of global food and livestock production, the main aspects of nanotechnology are improved quality and nutritional value. Conclusion and perspective Many diverse opportunities for nanotechnology exist to play an important role in agriculture and food production as well as in livestock production.
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In the first process, all the reactants are mixed together in a microwave tube in air atmosphere in contrast to the protective atmosphere of the hot-injection method [ ]. Then the tube is placed in a microwave reactor and the temperature is increased gradually. The shape of the all-inorganic metal halide nanocrystals synthesized by this method at high temperature are small cubes while they are plate-like for lower temperatures.
Ultra-thin nanowires are obtained when the precursors are pre-dissolved before increasing the temperature. The role of the trioctylphosphine oxide TOPO ligand is important in this reaction, it favors the dissolution of the precursors and thus helps to obtain high-quality nanocrystals. Besides, this reaction can take place at room temperature [ ]. In this case the ligand is bis 2,4,4-trimethylpentyl phosphinic acid TMPPA instead of oleic acid and the precursor is cesium acetate instead of cesium carbonate, and cubic nanocrystals of 19 nm in size are formed.
The type of the precursor plays an important role in the luminescence properties. Solid-state reaction or molten-salt methods have been extensively used for the synthesis of perovskite oxide nanocrystals. These two processes are easy and use simple equipment. The nanocrystals synthesized by such methods are well-crystallined but they have irregular shapes and wide size distribution. The solid-state process has been used to synthesize simple shapes such as irregular-shaped or spherical nanoparticles [ ], [ ], [ ], and only a few reports exist for nanocubes or nanowires [ ].
The starting materials are mixed together, a milling process is followed and then calcination at high temperature. In contrast, the molten-salt method has been proposed for various structures including irregular shapes [ ], [ ], [ ], [ ], [ ], [ ], morphologies of high-aspect ratio [ ], [ ], [ ], [ ] and platelets [ ]. In order to have a better control over the morphology than the previous methods, bottom-up solution-processed approaches have been realized including sol-gel, hydrothermal, solvothermal, sonochemical, or microwave-assisted reactions Table 1 , Figure 2.
Lower temperatures and in some cases organic ligands are utilized in such approaches. In these methods, a sol is formed when metal alkoxide, metal-organic, or metal-inorganic salt precursors are dissolved in an appropriate solvent, it is then dried and sintered at high temperatures.
The morphologies obtained by this approach are irregular-shaped [ 63 ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ] and spherical [ 64 ], [ ], [ ], [ ], [ ]. Only a few reports exist about this method for different structures such as cubic [ 64 ], [ ] or honeycomb-like [ ] structures. Reaction parameters which play important role on the morphology and the size of the synthesized nanocrystals are the temperature, time of the reaction, and heating rate [ ], as well as the usage or not of an organic ligand [ 64 ], [ ], [ ].
In order to save energy and to be cost effective, a sol-gel approach combined with a microwave-assisted sintering has been proposed for perovskite oxide nanocrystals [ ]. An aqueous suspension of insoluble salts is positioned in an autoclave and the temperature is increased. Precipitation from the solution of the crystalline material occurs at temperatures between the boiling point and the critical point of water. Various and more complex morphologies including randomly-shaped [ ], [ ], [ ], spheres [ ], [ ], [ ], [ ], [ ], cubes [ ], [ ], [ ], [ ], [ ], nanowires [ 67 ], nanotubes [ ], as well as more complex dendrite [ ] or star-like [ ] structures have been synthesized by this method compared to the simple structures synthesized by the sol-gel method.
A microwave-hydrothermal process has also been utilized for the synthesis of cubic perovskite oxide nanocrystals [ ]. The solvothermal method is a general procedure for perovskite oxide nanocrystals that are free of ligands. Lithium or barium metal was dissolved in benzyl alcohol at slightly elevated temperature. Benzyl alcohol has been proved to be a versatile solvent and reactant for controlled crystallization and stabilization of oxidic nanocrystals. The solvent polarity is crucial for the morphology control of the nanocrystals.
The nanocrystals can be spheres or cubes by tuning this parameter [ 66 ]. The size can also be tuned by changing the precursors concentration and the temperature of the reaction. This method has been used for the efficaciously synthesis of spherical [ 66 ], [ ], [ ], [ ], cubic [ 66 ], [ ] or even hollow [ 48 ] morphologies. These processes take place at room temperature, where all the reactants are dissolved in a solvent under ultra-sound irradiation.
With this method, irregular-shaped [ 65 ], [ ], spherical [ ], [ ], rods [ ], and polygons [ ] are fabricated. All of these nanocrystals are free of ligands. Metal halide nanocrystals of various morphologies and chemical phases have been used as absorber material in perovskite solar cells. Hybrid organic-inorganic lead halides of spheres [ ], [ ], nanosheets [ ] and nanowires [ ], [ ] have been used for active layer with the nanowires to show the higher efficiency to date Although, all-inorganic lead halides nanocrystals with spherical [ 16 ], [ ], [ ], [ ], [ ], cubic [ 15 ], [ ], [ ] and elongated [ ] morphologies have been used reaching an efficiency of In the case of the hybrid organic-inorganic solar cells, the efficiency was increased as the perovskite nanocrystal morphology changes from the spheres 2.
The use of nanowires in the photoactive layer is an effective way for enhancing light trapping and improving charge transport efficiency. For this reason, the charge separation and conductivity were higher in the case of the nanowires compared to the bulk film [ ], [ ]. Very recently nanowires synthesized from the same chemical phase synthesized by a two-step spin coating process have reached the value of the Partially developed perovskite nanowires in the photoactive layer contribute more to photocurrent generation than in compact films Figure 3E, F.
Later in , all-inorganic metal halide nanocrystals were used in perovskite solar cells instead of hybrid organic-inorganic materials to improve their stability [ 15 ], [ 16 ]. This high efficiency has been attributed to the stable cubic phase and not to the orthorhombic unstable phase in which the nanocubes are crystalline [ 15 ]. It is known that the CsPbI 3 chemical phase which exhibits the smallest band gap is not structurally stable in the bulk form.
Direct deposition of the CsPbI 3 nanocubes by spin casting, followed by stabilization of the perovskite structure via post deposition chemical treatment or annealing, contributed positively to the high quality of the active layer. The efficiency can be improved more and reach a value of The AX treatment provides a method for tuning the coupling among the nanocubes and improving the charge transport. The mobility of the treated film doubles, enabling an increased photocurrent and improved efficiency. These nanocubes showed a near unity photoluminescence PL quantum yield and improved chemical stability compared to the previous systems.
The ensuing nanocubes solar cells deliver PCE of In a different approach, all-inorganic metal halides have been introduced into the absorber MAPbI 3 layer to reduce charge recombination and improve the charge transfer [ ]. This process was used to improve the quality of the absorber layer in terms of film structure, morphology, and crystallinity as the nanocrystals behave as nucleation centers in the growth of perovskite films. The high quality of the films leads to improved charge transport and solar cell PCE.
At the same time, a protecting passivation layer of Cs 1-y MA y PbI 3-x Br x is formed on the top of the perovskite absorber layer and this contributes to the final stability of the solar cell. A champion PCE of Anion exchange at ambient conditions verified that this process could be an effective and simple way to obtain mixed halide nanocrystals and showed really promising results in perovskite solar cells [ ]. These perovskite solar cells displayed a photoconversion efficiency of 5. This method provides a new pathway for single-step, large-scale fabrication of inorganic perovskite solar cells.
These inks can be used directly to fabricate films of high optoelectronic quality. An active layer of nm prepared by nine sequential depositions, exhibited a PCE of 5. The treated film is uniform and compact after a surface dissolution-recrystallization process, with large grain size and low defect density. The recorded PCE by using this composite was 6. Finally, lead-free metal halide nanocrystals, free of toxic elements, were also introduced in perovskite solar cells.
Tin-based metal halide nanocrystals have been synthesized in the form of nanospheres [ ] or nanorods [ 60 ]. The efficiency of the devices using hybrid organic-inorganic tin halide nanospheres was 8. The highest solar cell performance was recorded for the device using the phase CsSnI 3 [ 60 ]. These nanorods exhibit colloidal stability in air for more than 2 months and a decomposition temperature significantly higher than that of MAPbI 3.
In addition, recently reported all inorganic bismuth-based cesium halide nanocrystals in the form of nanosheets of 4. The efficiency of this device was 3. Metal halide nanocrystals have been used at the interface between the perovskite absorbing layer and the HTL [ 17 ], [ 18 ]. The interface engineering is an effective way for obtaining high efficiency and improved stability in the perovskite solar cells through interfacial charge transfer control. In this way, an increased short-circuit current and an improved solar cell efficiency by In addition, the enhancement of the stability of perovskite solar cells can be attributed to the coating of the perovskite layer with the all inorganic CsPbI 3 , which has a high moisture stability and results in long-term stability of the perovskite solar cells in the air.
In order to make stable the hybrid organic-inorganic quantum dots, they are covered with a shell of C18 [ ]. These core-shell quantum dots — C18 were also used at the interface with the HTL. The presence of long chain ligands bound to the quantum dots did not appear to damage hole extraction.
Reproduced with permission from [ ]. Copyright , AAAS. B Schematic structure of the device using CsPbBr 3 -CsPb 2 Br 5 composite as an absorbed layer, fabrication process and comparison with fabricated layers at higher temperatures in the literature. Reprinted with permission from [ ]. All-inorganic metal halide nanocrystals have been employed as carrier blocking layers between the absorber layer of PbSe nanocrystals and the metal contact in dichalcogenide quantum dots sensitized solar cells [ ]. The relatively large E g 2. On the one hand, these nanocrystals have been chosen for their good air-stability, their high photoluminescence quantum yield and their ability to be synthesized independently and on the other hand, the quality of the perovskite layer seems not to be affected by the PbSe quantum dot layer.
The PCE of this solar cell configuration is 7. In a different approach, the metal halides were utilized as a passivation layer on the surface of the dichalcogenide quantum dots PbS forming a core-shell structure [ ], [ ], [ ]. A shell of hybrid organic-inorganic MAPbI 3 [ ], [ ] or all-inorganic CsPbI 3 [ ] metal halide was introduced for quantum dot passivation. In the first case, the film of the core-shell nanocrystals was incorporated in a photovoltaic device with graded band structure and recorded a PCE of 8. Two years later, a funtionalized quantum dot HTL was introduced in such structures to block the back flow of the photo-generated electrons, leading to enhanced photocurrent and fill factor compared to undoped devices [ ].
The ligand of the quantum dots was 1,2-ethanedithiol EDT and the solar cell performance reached the value of 9. The utilization of an all-inorganic shell around the PbS quantum dots led to a performance of In this case the shell was epitaxially grown on the core surface. The improved passivation significantly diminished the sub-bandgap trap-state-assisted recombination, leading to improved charge collection and therefore higher photovoltaic performance.
Irregular-shaped, free of ligands, hybrid organic-inorganic perovskite nanocrystals were used to enhance the light absorption of dye-sensitized solar cells employing liquid electrolytes [ ]. This incorporation resulted in a photovoltaic efficiency of 3. The gap between the electrodes was filled with an organic electrolyte solution containing lithium halide and halogen as a redox couple.
The perovskite nanocrystals were employed as charge-transfer bridge between the TiO 2 and the N dye to extract photo-induced charges from a light-harvester. This device showed the impressive power conversion efficiency of 7. Metal halide nanocrystals have been utilized for the improvement of the c-Si solar cell efficiency. Spherical organic-inorganic metal halide nanocrystals [ ] and all-inorganic nanocubes [ 19 ] have been used for such purposes with the second showing the higher performance.
Usually, these solar cells consume extra electric energy originated from an external bias. In this case by introducing the perovskite nanocrystals, the extra potential is generated by the light [ ]. The organometal trihalide nanocrystals synthesized by a low-temperature precipitation method are deposited on the top of the PEDOT:PSS top electrode and act as potential generation layer Figure 5A.
The device operates as a Schottky heterojunction solar cell with the light-induced electric polarization in the perovskite nanocrystals enhancing the electric field in the c-Si depletion region. The light harvested by organometal trihalide perovskite nanocrystals induces molecular alignment on a conducting polymer, which generates a positive electrical surface field. This device displayed a J sc of While the device without the perovskite nanocrystals exhibits a short circuit current J sc of B CsPbCl 1.
Reproduced with permission from [ 19 ]. The second report on using metal halide nanocrystals demonstrated a cheap, convenient, and effective way to enhance the PCE of the commercial silicon solar cells Figure 5B [ 19 ]. Doped all-inorganic metal halide nanocubes synthesized by a hot-injection method have been used as a downconverter of these solar cells due to their excellent quantum-cutting properties.
The PCE in this case is improved from They were self-assembled on the surface of the commercial single crystal silicon solar cell via liquid-phase deposition and the thickness was controlled ranging from 60 to nm. Compared to The best thickness of the nanocrystal layer is nm. The PCE of this device reaches to Irradiated by simulated AM 1. Perovskite oxide nanocrystals have been used as electron transporting materials. Films of sol-gel synthesized nanocrystals of Zn 2 SnO 4 have been utilized as ETLs for highly efficient perovskite solar cells [ ]. There is a dual role of these materials in perovskite solar cells.
The PCE in such perovskite solar cells leads the value of Furthermore, by replacing them with hydrothermally synthesized Zn 2 SnO 4 nanocrystals the performance has been further increased to a PCE of Structure and performance of flexible perovskite solar cells including Zn 2 SnO 4 nanocrystals as hole transporting layer.
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Energy levels of the materials B. Photocurrent density—voltage J—V curve measured by reverse scan with 10mV voltage steps and 40 ms delay times under AM 1. Copyright , Nature Publishing Group. Quite spherical perovskite nanocrystals have been used in ETL in dye sensitized solar cells due to their superior electron collection property. The energy conversion reported for such solar cells is 4. The electron capture in the perovskite oxide films was higher than in TiO 2 and the electron in the conduction band can diffuse rapidly resulting in greater photovoltaic performance.
The emission of CO 2 by human activities is an important factor for the dramatic change of the environment and phenomena such as the climate change and global warming. Photocatalytic reduction of CO 2 using solar energy into renewable hydrocarbon fuels has gained much attention in the effort to conserve energy [ 21 ]. By mimicking the natural photosynthesis in green plants, artificial conversion of CO 2 into chemical fuels such as carbon monoxide [CO], methane [CH 4 ], methanol [CH 3 OH], offers a promising approach to simultaneously mitigate the levels of greenhouse gas and produce renewable energy.
Nanocrystals of metal halides or perovskite oxides have been introduced as efficient photocatalysts for such purposes. Metal halides have not been applied for photochemical conversion water splitting or CO 2 reduction due to their instability in the presence of moisture or polar solvents. But there are some recent reports on novel photocatalysis to convert CO 2 into solar fuels in non-aqueous media. Single-phase lead-containing or lead-free metal halide nanocrystals have been proposed as novel catalysts for solar cell CO 2 reduction. A Single phase CsPbBr 3 nanocatalysts.
Reproduced with permission from [ 22 ]. Reprinted with permission from ref [ 24 ]. Under AM 1. The growth of the perovskite on GO results in the increase of the electron rate to These rates are superior compared to the common CdS quantum dots photocatalysts. These photocatalysts are stable after 12 h of photocatalytic reaction and no phase transformation or degradation are observed. The effective CO 2 reduction capacity 1.
The photocatalytic performance of the previous nanocomposite is improved when the metal halide nanocrystals were coupled with palladium nanosheets instead of GO Figure 7C [ ]. Their optimized performance in this case was Despite the poor photocatalytic behavior of the amorphous TiO 2 , its good chemical stability makes it good candidate as a protection layer for the lead halides.
The amorphous TiO 2 coverage has been witnessed as a pivotal driving force for preeminent photocatalytic performance by enhancing the extraction and separation of the photoinduced charges, and increasing the adsorption of the CO 2 simultaneously. Such combined effects finally boost the photoelectron consumption from Photocatalytic reduction of CO 2 to CH 4 is more thermodynamically favorable than the formation of CO and H 2 , which however, is kinetically challenging since eight electrons were involved.
NaNbO 3 and NaTaO 3 nanocrystals of similar size and synthesized by the same method have been tested as photocatalysts for the reduction of the CO 2 [ ]. Both perovskites give rise to the similar conversions in the CO 2 reduction reaction with a slightly higher carbon product evolution for the nanocrystals of NaTaO 3. Furthermore, the crystal structure of the nanocrystals seems to be a crucial factor for the photoreduction performance of the NaNbO 3 nanocrystals [ ].
The electronic structure of the cubic phase is beneficial for electron excitation and transfer. Furthermore, nanowires of the same chemical structure covered with the polymer g-C 3 N 4 showed an enhanced photocatalytic performance 8 times higher compared to the single-phase g-C 3 N 4 or the NaNbO 3 nanowires [ ].
BiWO 6 nanocrystals of different morphologies have been synthesized for photo-induced CO 2 reduction. Square BiWO 6 nanoplateles of 9. The ultrathin geometry of these nanocrystals also promotes charge carriers to move rapidly from the interior to the surface to participate in the photoreduction reaction and should also favor an improved separation of the photogenerated electron and hole and the lower electron-hole recombination rate. More complex nanosheet-based nanocrystals have been also designed to improve the catalytic performance.
Ball-flower-like nanostructures composed by nanoplatelets [ ] or nanoplatelets decorated with core-shell Au-CdS [ ] also synthesized for such purposes. Generating energy through thermoelectric materials is becoming increasingly important as the challenges faced nowadays in terms of energy production and efficiency are more intense than ever.
Much work has been carried out during the past decades in an effort to enhance the production of energy through novel materials and processes [ ], [ ], [ ]. Thermoelectric generators TEG constitute a new technology in order to recover heat which is based on the Seebeck effect and is broadly used for power generation.
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The Seebeck effect can be described as the connection of two different type p-type and n-type of conductors or semiconductors. This connection is formed by a parallel thermal connection along with an electrically connection in series which in turn causes a difference in voltage between the two materials [ ], [ ].
When connecting the two different components with a heated junction one can observe on the n-type component the transport of electrons from the hot junction to a heat sink whereas the p-type component transports holes which are positively charged, following the same direction as the temperature gradient. The efficiency that a specific material can possess in the conversion process of heat to electricity can be given by the formula below.
In order for thermoelectric materials to be competitive with ordinary power generators the figure of merit for TEG must be larger than 3 [ ], [ ]. Generally, finding materials with a ZT value above 2 is a challenging task but recent advancements [ ], [ ] in the effort to increase the figure of merit to around 3 has been made possible with the use of nanocomposites. In this direction, lead and tin halide perovskites namely CH 3 NH 3 PbI 3 and CH 3 NH 3 SnI 3 have been regarded as very promising photovoltaic materials mainly because of their relatively large absorption coefficient, high charge carrier mobility, and diffusion length properties [ ], [ ] also possessing a large Seebeck coefficient [ ], [ ].
Recent first principle studies of these materials have confirmed this and have provided detail insides especially when results are combined with the Rashba effect. This finding suggests that CH 3 NH 3 SnI 3 can constitute a very promising candidate for low cost and mass production processes. They reported a two-fold increase in the figure of merit which in turn is attributed to structural characteristics involving the existence of MnO 6 distorted octahedra.
This case is also interesting as two mechanisms are reported to occur simultaneously although their effect is canceling one another. The W doping seems to increase carrier concentration which ultimately leads to enhanced electrical conductivity and a decreased Seebeck coefficient. The enhanced electrical conductivity is a positive effect that outweighs the negative impact of the decreased Seebeck coefficient thus leading to an increased power factor.
This increase in ZT is also temperature depended and seems to increase almost linearly with increasing temperature. Overall the structural dependence of the ZT still remains a big challenge and is a promising field for more intensive research in order to elucidate the structural dependence of the above-mentioned phenomena. Emerging autonomous electronic devices require compaction and miniaturization of energy storage devices. Perovskite materials have received considerable attention for energy storage applications due to their excellent catalytic activity, electrical conductivity, and durability.
Ion migration through perovskite lattices allowing the use of such materials as electrodes for batteries. Electrochemical measurements on nanoparticulate perovskite systems showed that they displayed superior catalytic activity for oxygen reduction, as well as a higher discharge plateau and specific capacity compared to the bulk materials of the same crystal structure [ 29 ]. Perovskite oxide nanocrystals have been investigated for such application but in recent years metal halides have also shown high specific capacitance and promising stability upon cycling. This section summarizes all the reports on such applications focused on nanoparticulate systems of both metal halides and perovskite oxides and tries to correlate and understand the role of the size, the morphology and the intrinsic properties of the nanocrystals to the final performance of the batteries.
Hydrothermally grown organic-inorganic metal halide microcrystals were used as the active material in Li-ion storage devices presenting a discharge capacity of In this system, the capacity decreased rapidly in the first 30 cycles, it subsequently decayed slowly, showing a relative capacity retention of The discharge capacity for the first system was Two years later, CH 3 NH 3 PbBr 3 nanocrystals of 65 nm in size, synthesized by a precipitation method combined with a heating process, showed similar electrochemical response Figure 8A [ 31 ].
Very recently, the electrochemical performance of metal halide nanoparticulate electrodes by using aqueous electrolyte were evaluated by our group [ 32 ]. This is the first report of using metal halide nanocrystals in batteries using aqueous electrolytes. The nanocrystals were prepared at room temperature, by a fast, solution-processed co-precipitation method.
The electrodes were subjected to successive annealing cycles to optimize their electrochemical stability. The electrodes of five annealing cycles showed the best performance. A water-triggered transformation of the metal halide material occurred in the aqueous medium from Cs 4 PbBr 6 to CsPb 2 Br 5. Metal halide perovskite nanocrystals for Li-air batteries.
Electrochemical performance of the anodes consisted of A hybrid organic-inorganic CH 3 NH 3 PbBr 3 nanocrystals of 65 nm in size, synthesized by a precipitation method combined with a heating process and B all-inorganic metal halide, Cs 4 PbBr 6 nanohexagons of nm in size deposited on ITO electrodes and subjected to three and five cycles of thermal annealing. These layers are coated with a few-nanometer thin TiO x layer. A Reprinted with permission from [ 31 ].
B Reproduced from [ 32 ] with permission from the Royal Society of Chemistry. The overall capacity of the batteries is strongly dependent on the accessibility of the host material interior to the ions [ ]. Non-drastic structural alterations or rearrangements in the crystal lattice have been observed in this case. Using a combination of density functional theory and results by means of electrochemical characterization and diffraction techniques [ ], Li intercalation and conversion reactions in the CH 3 NH 3 PbX 3 where X: Br, Cl, I take place.
Furthermore, it was also found that the specific capacity is dependent on the crystal structure of the perovskite material [ ]. This could be improved by changing the dimensionality of the halide perovskites from three-dimensional 3D to a one-dimensional 1D lattice [ ]. Indeed, experiments on organic-inorganic hybrid lead halide perovskites showed that the Li intercalation in the two-dimensional 2D tetragonal structure is enhanced compared to the 3D orthorhombic one, due to the larger cell volume [ ]. Finally, the type of the anion plays role in the charging performance [ ].
It is observed that the Li intercalation is more favorable in the case of the iodides than in the chlorides or bromides [ ].
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The perovskite oxide nanocrystals started to be used in batteries from Later in , LaNiO 3 nanoparticles showed an improved cycling ability up to cycles [ ]. Single phase nanocrystals such as spherical or randomly-shaped [ 33 ], [ 34 ], [ 36 ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], [ ], nanocubes [ ], and anisotropic ones [ 38 ], [ 39 ], [ 40 ], [ 41 ], [ ], [ ] or bifunctional structures such as core-shell morphologies [ 42 ], decorated structures with a second material metal, carbon, or oxides [ 43 ], [ 44 ], [ 45 ], or composites [ 46 ] have been tested in order to improve the catalytic performance in batteries.
For example, nanocrystals synthesized by a ball-milling process showed superior catalytic activities compared to the nanocrystals without this process due to the structural change and defects in the crystal structure [ 33 ]. B-site doping in the manganite perovskite oxides La 0. Electrochemical performance of Li-air batteries including perovskite oxide nanocrystals.
Three factors that affect this performance are: Ni-doping in manganite perovskite oxide A , porosity of the nanocrystals LaNiO 3 nanocubes B , and synergetic effects in bifunctional nanocrystals La 0. A Reprinted with permission from [ ]. B Reproduced with permission from [ ]. Copyright , Springer. C Reprinted with permission from [ 45 ]. The morphology and also the porosity of the nanostructures affect the electrochemical performance, including the first discharge specific capacity, the overpotential, the rate capability, and the cycle stability.
Porous nanocubes Figure 9B [ ] or elongated nanocrystals nanorods or nanotubes or nanofibers [ 39 ], [ 40 ], [ 41 ], [ ] of perovskite oxides have been introduced for such purposes. Furthermore, bifunctional nanocrystals have been utilized to enhance the performance in metal-air batteries. Synergetic effect have been utilized to improve the catalytic activity by covering the La 0. The ORR takes place mainly at the core, while the OER takes place at the nanoscale shell and their synergetic effect leads to the enhanced catalytic performance.
Perovskites have found also use as electrode materials in supercapacitors for energy storage. A simple design of a supercapacitor is based on two electrodes separated by an ion-permeable membrane and an electrolyte ionically connecting to both electrodes. Supercapacitors are divided into three categories, the double-layer capacitors where the charge storage is electrostatically, the pseudocapacitors with electrochemically charge storage, and the hybrid ones which combine electrostatically and electrochemically charge storage [ ].
The nanodimensional perovskites that are used for such purposes are some metal oxides, a few nanocomposites and even more limited halides in contrast with the many reports for using all-inorganic or hybrid halides in photovoltaic applications. Many studies have been reported in lanthanum-based perovskite nanocrystals due to their structural stability at high temperatures and inherent nature to contain oxygen vacancies. Additionally, the structure of lanthanum-based perovskites allows the substitution of ions by other ions of varying oxidation states changing on demand the electronic and physical properties [ ].
Specifically, in LaMnO 3 nanocrystals by tuning the oxygen content, capacitance of Important also is the substitution of the B site ABO 3 in the perovskite crystal structure with elements such Mn, Fe, Cr, and Ni which leads to capacitances of Furthermore, among the lanthanum-based candidates for supercapacitors the perovskites with Ni in the B site hold a prominent role.
The incorporation of Ni offers excellent electrical conductivity and presents capacitances of a few hundred F. Specifically, LaNiO 3 nanosheets [ 49 ], hollow nanospheres [ 48 ], and randomly-shaped nanocrystals [ ] exhibit capacitance of Figure 10 shows their morphology and the cyclic voltammetry curves at different scan rates. LaNiO 3 perovskite nanocrystals for electrodes in supercapacitors with morphologies; A nanosheets, B hollow nanospheres, C irregular-shaped nanocrystals above figures and their cyclic voltammetry measurements at different scan rates below figures.
A Reproduced with permission from ref [ 49 ]. B Reproduced with permission from ref [ 48 ]. C Reproduced with permission from ref [ ]. A different type of lanthanum-based supercapacitor is that of incorporating composite materials. In this direction, a promising nanocomposite is the CeO 2 mixed LaMnO 3 which has been assessed as a negative electrode material [ ]. The advantage of such a mixture is the high surface to volume ratio of the CeO 2 nanocrystals which increases the active sites of the electrode.
Another interesting nanocomposite system is that which combines the LaMnO 3 with nitrogen-doped reduced graphene oxide N-rGO.
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In addition, the substitution of La atoms in the crystal structure of the perovskite with Sr gives very high specific capacitances. According to this, La 0. These values are among the highest reported for perovskites Figure Remarkably, the LSM15 NC nanocomposite in an asymmetric supercapacitor delivers energy density of The specific capacitance also increases slowly for the first cycles, becomes double above the cycles up to cycles.
This indicates the efficiency of this material for high performance supercapacitors. SEM images above figures and cyclic voltammograms below figures for A La 0. A Reproduced with permission from [ 47 ]. B Reproduced with permission from ref [ ]. Bimetallic Co-Mn and Ni-Co perovskite fluorides are also promising electrode materials for supercapacitors.
In an asymmetric capacitor design, it delivers 8—2. While the similar structure with Ni, KNi 0. Various oxide nanocrystals different than the previous have also been introduced for supercapacitor applications.
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Hydrogen, the most sustainable fuel offering higher efficiencies compared to diesel and gasoline, is compatible with fuel cells and produces renewal waste i. There are various hydrogen storage methods such as gas compression or liquefaction, however, they face safety issues. The most safe approach is the storage in solid-state materials such as metal alloys, metal oxides, hydroxides, carbon, chalcogenides, and recently in perovskites [ 51 ]. These nanocrystals formed aggregates with sizes ranging from 50 to nm [ 50 ].
The nanocrystals showed a higher discharge capacity than the bulk counterparts of the same stoichiometry. The discharge capacity is a value which characterizes the hydrogen storage efficiency of a material and it is estimated by the galvanostatic behavior of charge and discharge. In this method the investigated material was deposited on the electrode and circles of charges and discharges were followed [ 51 ]. In the case of nanostructured LaFeO 3 , the discharge capacity reaches the value of However, the LaFeO 3 nanostructures showed higher current densities and hydrogen diffusion coefficients.
Decreasing the size of the nanostructures is expected to increase the discharge capacity due to the larger surface area. The proposed mechanism of hydrogen storage lies in a two-step reaction. The first step takes place on the surface of the material over a few atomic layers, while the second occurs inside as the H-atoms are diffused [ ]. Although, these studies mentioned that the structural defects may play role in the storage capability, their exact role on the final performance are not yet clear.
Also, it would be interesting to study newly solution-processed metal halide nanocrystals in such storage applications. A LaFeO 3 nanocrystals. Reproduced with permission from [ 50 ]. Copyright , American Institute of Physics. B DyFeO 3 nanocrystals. C Ba 2 Co 9 O 14 nanocrystals. In recent years the perovskite nanocrystals have been introduced to effectively replace conventional energy materials.
The simultaneous need for new energy materials together with the increasing interest for the development of new devices and even exploring new physics, have pushed the research to manipulate the structuring of the perovskite materials at the nanoscale level. The nanostructuring of the perovskites due to their reduced dimensions is advantageous in offering a large surface area, extensive porous structures, controlled transport, and high charge-carrier mobility, strong absorption, and photoluminescence, and confinement effects. In recent year there is a lot of work incorporating them into photovoltaics as active materials or covering the active layer to improve its stability but there has been limited effort to use them as thermoelectric materials or photocatalysts for the CO 2 reduction in solar fuel cells.
The utilization of them in CO 2 reduction is a completely new scientific field which has gained increased interest very recently. In addition, perovskite nanocrystals have received considerable attention for energy storage applications due to their excellent catalytic activity, electrical conductivity, and durability. Ion migration through perovskite lattices allows the use of such materials as electrodes for batteries or supercapacitors.
Perovskite oxide nanostructures are more investigated for such applications but very recently the metal halides have also shown high specific capacitance and promising stability upon cycling. Finally, the utilization of such nanocrystals in hydrogen storage could be really interesting as hydrogen is the most abundant element on the planet, with the highest energy content amongst all the existing energy sources, but the number of the perovskite nanocrystals used for such purposes is still limited.
This review article has covered many aspects of the synthesis of nanocrystals made of metal halides or perovskite oxides, but also their applications in energy conversion and storage. Despite the important evolution in the synthesis procedures, there are some open issues which require attention when we use these materials in these applications. Some of these open issues are:. Despite the huge evolution of synthesis strategies for the fabrication of nanocrystals of different morphologies and chemical phases, there is a poor understanding of the role of the ligands on the nanocrystal quality concerning their stability, carrier transport, but also on the energy device performance in which are included [ ].
It is not clear if the ligands passivate structure trap states or introduce new ones and how the crystal defects play a role in the whole reactivity and electronic properties of the passivated nanocrystals. Long-term stability issues at ambient conditions or more harsh environments such as high temperature, direct irradiation, light, and humidity have to be carefully addressed when we are interested in industrial applications.
The careful choice of a protective ligand has been proposed as an effective way to improve the stability of the nanocrystals but the effect on device performance is something that has to be studied. The encapsulation of the nanocrystals in a matrix or a different material could be another way, but it is still unknown if such shelling could really prevent the nanocrystals from oxygen and moisture [ 12 ].
Finally, all-inorganic metal halides or lead-free compounds could effectively improve the stability of the devices, but still the performance of these devices remains very low. The synthesis of lead-free and environmentally friendly nanocrystals is a demand. Tin- or bismuth-based compounds have been introduced as possible stoichiometries and more recently double perovskites with an elpasolite structure [ ]. The synthesis approaches for these perovskite nanocrystals remain limited.
Only a few reports exist for elpasolite nanocrystals and all these nanocrystals are of spherical morphology and capped with organic ligands. The performance of bismuth based solar cells remains is very low. One of the drawbacks of the synthesis procedures reported in this review is the small quantity of the final product. The development of large-scale synthesis procedures which will be cheap and easy is still a real challenge. Perovskite nanocrystals have been used in energy applications due to their large surface area, efficient carrier transport, high absorption coefficient, long-term stability, and tunable bandgap.
The morphology and crystallinity are some of the important intrinsic features that affect the final performance of the devices. But in most of the applications these nanocrystals are assembled in films. The shape and size of the nanocrystals and the existence or not of ligands on the surface determine the final structure of the film. The formation of compact and smooth films is a real challenge for such applications.
Many methods for the fabrication of films of high quality free of pinholes and cracks have been proposed, but many parameters remain unexplored and have to be controlled. The removal of the capping ligands is a necessity in order to fabricate such films with enhanced electrical properties. For such purposes, various methods for this removal have been proposed, but many times they are insufficient which result in the release of nanocrystals from the surface or cause their undesired growth of the nanocrystals.
These affect also the stability of the devices in which are utilized such nanocrystals. The development of new efficient strategies for the effective removal of the capping ligands without affecting their primary structural or morphological features is a requirement. Accordingly, it is important here to comment on attempts such as the encapsulation of perovskite nanocrystals in perovskite matrices [ ] or the incorporation of nanocrystals between the active layer and the hole transporting layer [ 17 ], [ 18 ].
Interface engineering is an effective way for obtaining high efficiency and improved stability in the perovskite solar cells through interfacial charge transfer control. In addition, perovskite nanocrystals have been introduced into the absorber layer to reduce charge recombination and improve the charge transfer [ ]. This process used to improve the quality of the absorber layer in terms of film structure, morphology, and crystallinity as the nanocrystals behave as nucleation centers in the growth of perovskite films.
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