Engineering halide perovskites for artificial leaves
Lead Research Organisation:
University of Bath
Department Name: Chemical Engineering
Abstract
The manufacturing of artificial leaves that reproduces at larger scale what plants do when they form carbohydrates by natural photosynthesis is a grand ambition for the creation of a sustainable society. Success has the potential to cease our dependence on fossil sources for polymer syntheses, pharmaceutical manufacture, and transport applications (e.g. fuels in cars) and instead allow us to use atmospheric or flue gas CO2. The Royal Society of Chemistry emphasises this potential in the recently launched report "Solar Fuels and Artificial Photosynthesis" (2012). In line with this, the US Department of Energy has identified the photo-driven conversion of CO2 as a priority research direction and The Institution of Chemical Engineers (IChemE) has recently launched a new special interest group dedicated to alternative and renewable energy.
Many active semiconductor photocatalysts such as titania and zinc oxide have been proven to photocatalytically convert CO2. However, they offer low yields of products under sun irradiation due to their intrinsic limitations such as low solar absorption and short lifetime of photoinduced charges. To make CO2 solar photocatalytic reduction a viable and commercial technology further research on novel materials is needed.
This research project aims to develop artificial leaves with halide perovskites, novel materials of unprecedented success in photovoltaics that remain unexplored in photocatalysis because they suffer from chemical and structural instability. We will develop smart approaches to protect them from decomposition using conductive layers and moreover design and optimise the reactors and reaction conditions that favour their photocatalytic activity as well as their preservation. This way halide perovskites will become a new front-runner in the field of photocatalysis, ensuring important advances towards a more sustainable mix of clean energy and feedstocks for current and future generations.
Many active semiconductor photocatalysts such as titania and zinc oxide have been proven to photocatalytically convert CO2. However, they offer low yields of products under sun irradiation due to their intrinsic limitations such as low solar absorption and short lifetime of photoinduced charges. To make CO2 solar photocatalytic reduction a viable and commercial technology further research on novel materials is needed.
This research project aims to develop artificial leaves with halide perovskites, novel materials of unprecedented success in photovoltaics that remain unexplored in photocatalysis because they suffer from chemical and structural instability. We will develop smart approaches to protect them from decomposition using conductive layers and moreover design and optimise the reactors and reaction conditions that favour their photocatalytic activity as well as their preservation. This way halide perovskites will become a new front-runner in the field of photocatalysis, ensuring important advances towards a more sustainable mix of clean energy and feedstocks for current and future generations.
Planned Impact
Academics and centres conducting research in the renewable energy and catalysis sector will be the primary beneficiaries of this research, since they will benefit from the research outcomes on using halide perovskites to photocatalytically convert CO2 to commodity chemicals. They will benefit from the novel protocols developed to stabilise perovskites as well as from their characterisation and development, which they will be able to apply to their research to progress further. Academics broadly in chemical engineering will also benefit from novel catalysts and optimised reactors for CO2 reactions and sun utilisation.
Companies will benefit from the novel protocols developed to prepare more resistant halide perovskites for photocatalysis and from the design and development of more efficient photocatalytic reactors. In addition to contributing towards the creation of more efficient devices that use clean energy (sun), there will also be opportunities to apply both the novel materials in other technologies such as photovoltaics, lasing, sensors and diodes and the novel reactors in other technologies such as water treatment.
The general public will benefit from this research with next generation materials that produce commodity chemicals from simply sun, CO2 and water, diversifying the energy portfolio and feedstocks sources. The results of this research aim to contribute towards a more sustainable society, a circular economy, and a cleaner and healthier environment.
Companies will benefit from the novel protocols developed to prepare more resistant halide perovskites for photocatalysis and from the design and development of more efficient photocatalytic reactors. In addition to contributing towards the creation of more efficient devices that use clean energy (sun), there will also be opportunities to apply both the novel materials in other technologies such as photovoltaics, lasing, sensors and diodes and the novel reactors in other technologies such as water treatment.
The general public will benefit from this research with next generation materials that produce commodity chemicals from simply sun, CO2 and water, diversifying the energy portfolio and feedstocks sources. The results of this research aim to contribute towards a more sustainable society, a circular economy, and a cleaner and healthier environment.
Organisations
People |
ORCID iD |
| Salvador Eslava (Principal Investigator) |
Publications
Kumar N
(2020)
Polypyrrole-Promoted rGO-MoS 2 Nanocomposites for Enhanced Photocatalytic Conversion of CO 2 and H 2 O to CO, CH 4 , and H 2 Products
in ACS Applied Energy Materials
Kumar S
(2021)
Mechanochemically synthesized Pb-free halide perovskite-based Cs 2 AgBiBr 6 -Cu-RGO nanocomposite for photocatalytic CO 2 reduction
in Journal of Materials Chemistry A
Kumar S
(2020)
All-Inorganic CsPbBr 3 Nanocrystals: Gram-Scale Mechanochemical Synthesis and Selective Photocatalytic CO 2 Reduction to Methane
in ACS Applied Energy Materials
Poli I
(2019)
Graphite-protected CsPbBr3 perovskite photoanodes functionalised with water oxidation catalyst for oxygen evolution in water.
in Nature communications
Schukraft GEM
(2021)
Hypercrosslinked Polymers as a Photocatalytic Platform for Visible-Light-Driven CO2 Photoreduction Using H2 O.
in ChemSusChem
Sharma N
(2019)
Photocatalytic Activation and Reduction of CO 2 to CH 4 over Single Phase Nano Cu 3 SnS 4 : A Combined Experimental and Theoretical Study
in ACS Applied Energy Materials
Temerov F
(2020)
Silver-Decorated TiO2 Inverse Opal Structure for Visible Light-Induced Photocatalytic Degradation of Organic Pollutants and Hydrogen Evolution.
in ACS applied materials & interfaces
Temerov F
(2022)
A Review on Halide Perovskite-Based Photocatalysts: Key Factors and Challenges.
in ACS applied energy materials
Zhang Y
(2019)
Pyro-electrolytic water splitting for hydrogen generation
in Nano Energy
| Description | Thanks to this grant, my group has been able to demonstrate a fast and convenient mechanochemical synthesis of CsPbBr3 perovskite nanocrystals with scale-up capability and control over crystal size and morphology (Kumar et al., ACS Appl. Energy Mater. 2020). These perovskite nanocrystals show excellent crystallinity and tuneable morphologies, from nanorods to nanospheres and nanosheets, simply changing the mechanochemical reaction conditions such as ball milling time, ball size and Cs precursor. The obtained perovskite nanosheets photocatalytically convert CO2 and H2O(g) in gaseous reactors under "1 sun" of simulated sunlight to 0.45 µmol CH4 g 1 h 1, 2.03 µmol CO g-1 h-1, 0.09 µmol H2 g-1 h-1, and stoichiometric amount of O2, with a 30% retention of activity over three consecutive cycles. We avoid the use of expensive organic solvents as a medium or hole scavengers. Importantly, we have discovered that the mechanochemical synthesis of these CsPbBr3 nanosheets together with Cu-loaded RGO results in a 6-fold improvement in the photocatalytic activity to 13.1 µmol CH4 g-1 h-1, 0.45 µmol CO g-1 h-1 and 0.23 µmol H2 g-1 h-1, with a 90% retention of this activity over three consecutive cycles. The selectivity for CH4 increases to 98.5% on an electron basis and a remarkable apparent quantum efficiency of 1.26% at 523 nm is achieved. Synergistic effects between all the components of the CsPbBr3-Cu-RGO composites are observed, resulting in a boost to the activity, selectivity for CH4, and stability while the hydrophobic RGO limits the perovskites deterioration due to moisture and promotes an increased CO2 adsorption via p-p interactions. Recently, we have extended this work to lead-free halide perovskites, specifically Cs2AgBiBr6 forming composites with Cu-RGO and obtaining comparable results. We have also developed a novel halide perovskite CsPbBr3 photoanode for H2O oxidation, using an inexpensive strategy to stabilise them with carbon layers to be readily used in aqueous electrolytes (Poli et al., Nature Comm. 2019. Using our previous developed knowledge on semiconductors and graphene/graphite materials, we exploited smart architectures which included hydrophobic, inexpensive, conductive and catalytic components. The inexpensive carbon layers consisted of a mesoporous carbon layer and a self-adhesive graphite sheet, both hydrophobic, whose role was to protect the halide perovskite from otherwise immediate degradation in aqueous electrolytes while holes were allowed to travel through to reach the aqueous electrolyte. We achieved 80% faradaic efficiency observing vigorous oxygen bubbles evolving. Moreover, the graphite sheet was easily complemented with catalysts - we added here an Ir electrocatalyst lowering the H2O oxidation overpotential around 100 mV but more inexpensive electrocatalysts would also work. Under this configuration, our halide perovskite device achieved a record stability of 30 h evolving oxygen at 1.23 V vs. RHE in an aqueous electrolyte under simulated sunlight with photocurrents above 2 mA cm-2 at 1.23 VRHE and a potential onset of 0.5 VRHE. |
| Exploitation Route | These results, together with other results also published under this grant, have contributed to the advance on the generation of solar fuels and will open new avenues for future progress. Our work is receiving tens of citations, showing their importance to advance in this field. |
| Sectors | Chemicals,Creative Economy,Energy,Environment,Manufacturing, including Industrial Biotechology |
| URL | https://pubs.acs.org/doi/10.1021/acsaem.0c00195 |
| Description | Our research outcomes has contributed to the development of a novel material that is revolutionising the field of solar harvesting and utilisation. These outcomes are having an academic impact on the field of solar devices, as it can be seen in the scientific literature, conferences and further funding achieved. Our research is also impacting companies that have benefited from the know-how generated .For example, we are working together with companies to develop other types of perovskites for photocathodes for hydrogen generation. All this research is contributing to a knowledge society that is facing global challenges such as climate change and pollution. We are keeping our society informed with outreach events, for example the Great Exhibition Road Festival |
| First Year Of Impact | 2018 |
| Sector | Chemicals,Creative Economy,Energy,Environment,Manufacturing, including Industrial Biotechology |
| Impact Types | Societal,Economic,Policy & public services |
| Description | Interface Engineering for Solar Fuels |
| Amount | £1,056,131 (GBP) |
| Funding ID | EP/S030727/1 |
| Organisation | Engineering and Physical Sciences Research Council (EPSRC) |
| Sector | Public |
| Country | United Kingdom |
| Start | 07/2019 |
| End | 07/2024 |