Artificial photosynthesis: On overview of current challenges technological characteristics

on future prospects

Submitted By: Bibi Sapna

This review paper is submitted for the Degree of bachelor science in chemistry

Supervisor: Ma’am Shereen

Department of chemistry
Govt Girls Postgraduate College Quetta Cantt

Session 2020-2024
Introduction

Artificial Photosynthesis
As natural resources dwindle and environmental pollution worsens, there is a pressing need
for renewable and carbon-neutral energy sources ( Purchase, et al., 2015). Solar, wind, and tidal
power are viable alternatives as they generate electricity, though they necessitate specific
infrastructure for storage and distribution. However, implementing these technologies may pose
challenges in regions with diverse socio-economic backgrounds or unique
environmental characteristics (Furugori, et al.,2017). Furthermore, harnessing sustainable energy
from these sources can result in adverse local environmental impacts. For instance, hydroelectric
power plants can cause flooding and alter water temperature and flow patterns,
disrupting (Tiwari, et al.,2015). Wind power systems have also been documented to cause harm
to wildlife. In contrast, traditional chemical fuels, long relied upon for their high energy density,
stability, portability, and the extensive existing infrastructure, are often considered more practical
for many applications (Li, et al.,2016). Therefore, storing energy in chemical bonds represents
the optimal approach to energy storage and (Zhang, etal.,2019)

Figure 1. illustrates a schematic representation of how carbon dioxide can be recycled

into fuel (Barber, et al.,2013).

Researchers achieved two objectives by mimicking natural photosynthesis: they harnessed

energy from renewable sources and stored it in chemical bonds. In natural photosynthesis,
sunlight triggers oxidation and reduction reactions that convert water and carbon dioxide into
oxygen and (Zong, et al.,2005). Artificial photosynthesis replicates natural processes to harness
solar power, the most abundant and widely distributed form of renewable energy
on Earth (Zhao, et al.,2018). It converts carbon dioxide directly into durable and transportable
chemical fuels. Besides its exceptional storability, artificial photosynthesis also provides
environmental benefits (Wang, et al.,2020). This technology recycles atmospheric CO 2 to
produce carbon-based fuels, thereby reducing the carbon footprint associated with fuel usage.
Simultaneously, it releases oxygen into the ecosystem, contributing to environmental
sustainability (Figure 1) (Smith, et al.,2020). Artificial photosynthesis is pivotal for achieving a
clean energy future. While solar energy conversion is not a new concept and laboratory-scale
feasibility of artificial photosynthesis has been demonstrated, significant technical
challenges (Zhao et al.,2019). Overcoming these challenges is essential for researchers to
establish cost-effective and industrially viable methods to convert sunlight into fuel.

Appropriate of artificial photosythesis

 In natural photosynthesis, antenna molecules such as chlorophyll, carotene, and other
pigments are responsible for capturing sunlight, facilitating four key processes: light harvesting,
charge separation, water splitting, and fuel (Cheng, et al.,2020). This energy is subsequently
transferred to the photosystem II of plants, algae, or cyanobacteria, where it excites an electron
within the antenna molecule. This initiation of electron transfer sequences leads to the separation
of positive and negative (Janaky, et al.,2020).

The positive charges generated are employed to initiate the water splitting process (water
oxidation), which produces hydrogen ions and (Peter, et al.,2019)Meanwhile, the electrons, in
conjunction with the hydrogen ions and additional electrons released during earlier water
oxidation stages, are utilized to convert carbon dioxide into (Li,R et al.,2017). In an artificial
photosynthesis system, researchers employ a photosensitizer to capture solar energy. This energy
is then transferred to a reaction center to initiate the charge separation process (Zong, et
al.,2015). Positive charges subsequently initiate water oxidation at the catalytic center, resulting
in the production of hydrogen ions and oxygen (Purchase, et al.,2015).

At this stage, the collected hydrogen gas is readily captured. While hydrogen is a promising
energy carrier, further research aims to advance the creation of carbon-based (Furugori, et
al.,2017).

These fuels offer advantages over hydrogen gas, including easier storage,
transportation, and also because their production recycles excess CO 2 in the (Ciamician,G. et
al.,2019). Possible fuel products that could be generated include carbon monoxide (CO),
methane (CH4), methanol (CH3OH), and formic acid (HCOOH)(Akira et al.,2020). These
carbon-based fuels offer the additional benefit of recycling excess CO 2 from the atmosphere. To
transform artificial photosynthesis into a practical application, scientists and engineers have
developed a system comprising a light-harvesting device and a reaction center for catalyzing
water oxidation and CO2 conversion (Abe,R et al.,2022). It is crucial for these components to be
integrated in a manner that maximizes energy efficiency.

In natural photosynthesis, solar energy can be lost through wavelength degradation,

saturation processes, and most significantly, through fueling a series of reactions within the
photosynthetic organism necessary for the plant's survival (Bard,A et al.,2016). The theoretical
maximum efficiency of photosynthesis is estimated to be 4.5%; however, achieving this
maximum efficiency is rare, and most of the time, efficiency levels are below 1%. Factors such
as seasonal changes and the presence of non-agricultural land and ocean greatly reduce the
overall efficiency of photosynthetic (Ciamician,G. et al.,2019). Although there are efforts to
engineer plants and other photosynthetic organisms for higher efficiency, achieving efficiencies
above 1% in these attempts is uncommon Energy conversion technologies hold the promise of
achieving significantly higher efficiencies if developed (Chen, D. et al.,2015)

While artificial photosynthesis systems typically require a minimum efficiency of 10% to

be industrially feasible, Bio Solar Cells, a Dutch research program, has projected a theoretical
efficiency of up to 40% for their system. Artificial photosynthesis systems not only need to
achieve the desired efficiency but also must be durable enough to withstand extreme weather
conditions and cost-effective enough to achieve commercial viability (Yang,D. et
al.,2013). Addressing the durability challenge can be approached through two potential
solutions: the materials used in constructing the system must be highly durable, or alternatively,
the system itself should possess self-repairing capabilities when damaged (Yang, et al.,2015).. To
enhance the widespread applicability of artificial photosynthesis, it is essential to minimize the
use of rare and expensive materials to optimize cost-efficiency (Hill, et al.,2018). Numerous
standalone prototypes of artificial photosynthesis systems have been developed, with ongoing
efforts focused on enhancing their durability, energy efficiency, and cost-effectiveness to meet
desired (Wydrzynski, et al.,2014).

Challenges of artificial photosynthesis

1. Access to light harvesting

Rather than utilizing natural antenna molecules found in plants, an artificial system captures
solar energy using photosensitizers or light absorbers, such as semiconductors, molecular dyes,
or quantum dot (Boekema, et al.,2012). The pioneering invention involved using titanium oxide
(TiO2) as a light absorber and catalyst for solar water splitting. However, TiO 2 can only absorb
ultraviolet light, and therefore cannot efficiently harvest the full spectrum of (Jarvis, et al.,2015).
One approach researchers have employed to address this limitation is sensitizing the
TiO2 electrode with a dye sensitizer. the semiconductor substrate (in this case TiO 2), which
enhances electron transfer and thereby improves charge separation (Van Rensen, et al,.2013).

Since titanium oxide has shown limitations in light-absorbing efficiency, researchers have
explored alternative materials as light-harvesting semiconductors(Day,. One particularly
promising alternative is silicon, known for its abundance, affordability, and capacity to
efficiently absorb and store energy (Tiwari, et al,.2015). Other semiconductors, both oxide and
non-oxide, have been extensively studied. These materials encompass metal oxides like ZnO,
Fe2O3, and BiVO4, as well as metal nitrides such as Ta 3N5, and metal oxynitrides like TaON.
Fe2O3 photoelectrodes, in particular, have garnered significant interest due to their narrow band
gaps, high stability, and cost-effectiveness (Haumann, et al,.2015).

2. Access to catalytic reaction

In natural photosynthesis, chlorophyll and other antenna molecules, along with bacteria, serve
as catalysts for the conversion of water and carbon dioxide into oxygen
and carbohydrates (McEvoy, et al,.2016). This process harnesses light energy to drive
biochemical reactions essential for sustaining lif Efforts to replicate the functions of natural
components with man-made catalysts often involve developing and enhancing these catalysts to
scale up artificial photosynthesis techniques(Kok, et al ,.202017). This includes improving their
activity, stability, selectivity, cost-effectiveness, and energetic effeciency (Heyduk, et al,.2011).
Researchers study three main catalytic approaches for water splitting and fuel production
processes. material catalysts typically consist of bulk or nano particulate solids, often composed
of metals or semiconductors (Konduri, et al,.2012). These catalysts are heterogeneous in nature
and typically exhibit a distribution of active sites. In contrast, biological catalysts refer to
enzymes or microorganisms, including both natural variants and genetically
modified forms (Pellegrin, et al,.2018).

Molecular catalysts typically involve a metal center serving as the active site, around which
organic ligands are arranged to create an environment that regulates the activity of
the catalyst (Born, et al,.2015). These characteristics provide molecular catalysts with several
distinct advantages. They often exhibit a well-defined structure with identifiable active sites and
catalytic mechanisms. Additionally, the design of ligands enables precise adjustments to the
molecular complexes, including modifications to steric configuration and
electronic structure (Astruc, et al,.2017).

Molecular catalysts enhance electrode activity by improving the selectivity of the

CO2 reduction reaction. At the molecular level, these catalysts can fully exploit the activity of
metal atoms, giving them an advantage over material-based counterparts (Whang, et al,.2015).

Over the past three decades, extensive research has focused on molecular catalysts, leading
to significant advancements in their synthesis and effectiveness (Kobayashi, et al,.2012). This
includes innovations in ligand design, as well as advancements in the synthesis and
characterization of both ligands and the final metal complexes (Kitamoto, et al,.2014). Recent
research has yielded fruitful results in the synthesis, catalytic analysis, and elucidation of
mechanisms across a diverse array of materials, ranging from the rare noble metals like Ru
and Ir to more abundant (Lin, et al,.2016).

Earth elements such as Mn, Co, Cu, and Fe. Researchers have identified the next critical
advancement in the field of artificial photosynthesis (Molnar, et al,.2014). the heterogenization of
molecular catalyst. If molecular catalysts can be effectively immobilized on a solid support
without aggregation, while preserving their advantageous structural characteristics and activity, it
could represent a significant stride towards developing practical artificial
photosynthesis devices (Zigler, et al,.2018). Recent biotechnology research has explored the use
of halo-tolerant bacteria as electrocatalysts in bio-electrochemical systems operating underwater,
leveraging their self-sustainability and renewability as advantageous traits (Arachchige, et
al,.2019). However,the current output obtained from such systems is relatively low due to the
energy required by these bacteria to sustain their metabolism and function effectively in the
harsh saline environments. Energy losses due to the self-sustainment of bacteria must be
considered if living organisms were to be integrated into artificial photosynthesis system (Ranga,
et al,.2019).

Alternatively, enzymes such as hydrogenase have also been explored for their capability to
activate hydrogen evolution in the design of artificial photosynthesis (Kitamoto, et
al,.2014).Unfortunately, scaling up hydrogenases for practical applications has proven
challenging due to their sensitivity to oxygen and lack of robustness for long-term operation.
Moreover, difficulties in large-scale cultivation of the required organisms further complicate
techniques involving biological catalysis (Elvington, et al,.2016).
Catalytic access to water oxidation
Water oxidation, or the process of water splitting, can be described by the
chemical reaction (Zigler, et al,.2018).
2H2O 4e⁻ + 4H⁺ + O2

The transfer of 4 protons and 4 electrons necessitates a substantial thermodynamic

potential and a significant over potential to overcome the considerable kinetic
barrier involved (Ranga, et al,.2019). In nature, the reaction is facilitated by the oxygen-evolving
complex within photosystem II. Researchers' current grasp of this complex's structure and
function shapes their evolving understanding of the mechanism behind water oxidation,
potentially paving the way for the development of synthetic alternatives to this
natural process (White, et al,.2011).

Understanding nature's method of water oxidation could serve as a model for designing
efficient catalysts in artificial photosynthesis (Still, et al,.2013). Figure 2 depicts the water
oxidation process in three typical devices used in artificial photosynthesis research (Stoll, et
al,.2013).

Water-oxidation catalysts (WOCs) currently being developed are complexes based on

redox-active transition metals, where the unsaturated first coordination spheres serve as catalytic
active sites (Johansson, et al,.2013). Ruthenium-based WOCs, such as the dinuclear ruthenium
complex (commonly known as the blue dimer), represent the earliest molecular
WOCs studied (Sun, et al,.2016). Since then, numerous binuclear ruthenium-based WOCs were
developed until 2005, when the Thummel group introduced a series of mononuclear
ruthenium WOCs (Collomb, et al,.2019). This discovery suggested that a single metal active
center is sufficient for catalyzing water oxidation. This represented a significant advancement in
the study of molecular water-oxidation catalysts (WOCs) (Romain, et al,.2016). Ir-based
complexes constitute another traditional category of water-oxidation catalysts (WOCs). Research
on single-atom catalysts comprises a substantial portion of studies on Ir-based catalysts, whereas
catalysts involving two or more atoms are less explored due to significant challenges in
synthesizing such structures (Karlsson, et al,.2010). In 2018, the successful synthesis of
iridium dinuclear heterogeneous catalysts (DHCs) was reported, demonstrating exceptional
stability against detachment and aggregation, along with high activity for
water oxidation (Niyogi, et al,.2012).

Despite significant development over three decades, both ruthenium-based and iridium-
based water-oxidation catalysts (WOCs) remain impractical for large-scale applications due to
their high cost and limited (Demmig, et al,.2019). The quest for a cost-effective artificial
photosynthesis device necessitates the use of molecular water-oxidation catalysts (WOCs) based
on earth-abundant transition .metals (Krause, et al,.2015). Since research on such earth-abundant
molecular WOCs commenced in the 2010s, advancements have been made towards developing
WOCs from manganese (Mn), cobalt (Co), nickel (Ni), copper (Cu), and iron (Fe).Regrettably,
the activity rates of these economically viable options remain significantly low. Developing
water-oxidation catalysts (WOCs) that are both cost-effective and highly efficient for large-scale
applications remains a formidable challenge that necessitates further research (Barber, et
al,.2019).

Catazlytic access to CO2 reduction

Unlike the situation with water-oxidation catalysts (WOCs), the development of earth-
abundant molecular CO2-reduction catalysts (CO2RCs) has seen significant success (Demmig, et
al,.2010). Transition metal complexes such as those containing Re, Ru, Ir, Co, Ni, Mn, Fe, and
Cu have been widely researched for their ability to catalyze the reduction of CO 2 under both
electrochemical and photochemical Conditions (Aro, et al,.2019).

Transition metal complexes including Mn-bipyridine, Fe porphyrins, binuclear copper

complexes, metal corroles, and even metal-free pyridinium ions have been investigated as
catalysts for CO2 reduction (Barber, et al,.2019). In 2017, a cobalt chlorine complex was
successfully integrated into a photoelectrochemicalsystem to catalyze CO 2 reduction, achieving a
high faradaic efficiency of 83% for CO production. However, these systems still exhibit
relatively low overall (or solar-to-fuel) efficiency and quantum yield. They rarely have the
capability to produce multielectron-reduced products such as methanol or methane (Zhang, et
al.,2019).

Figure 3 in Janáky and He's 2020 study presents statistical analyses of CO2 conversion
in photoelectrochemical devices: (a) distribution of product types and (b) distribution of
Faradaic efficiencies (Foyer, et al,.2019).

The photoelectrochemical cell (PEC) represents one of the two primary categories of
devices employed in solar energy conversion. Researchers have conducted a statistical analysis
on various contemporary studies focusing on CO 2 conversion in PECs (Janáky, et
al,.2020). Figure 3 illustrates the distribution of carbon-based fuel products and Faradaic
efficiency (FE) in a dataset encompassing 60 cases. Approximately 38.3% of these cases resulted
in the production of HCOOH, while 36.7% yielded CO (Horton, et al,.2014). The production
of multielectron-reduced chemicals such as CH 4 and CH3OH occurred in only a small fraction of
the cases. Most studies achieved high Faradaic efficiencies, with over 60% reporting FE values
above 60%, and 32% achieving an FE higher than 80% (Long, et al,.2018). This statistical
analysis aligns with findings by Zhang and colleagues. Sun's review paper highlighted that while
researchers have made notable advancements in improving Faradaic efficiency, fewer have
succeeded in generating multielectron-reduced chemicals. A significant limitation identified in
contemporary research is the incomplete understanding of CO 2 transformation mechanisms at the
cobalt (Krause, et al,.2011).

The mechanism of CO2 reduction at the catalyst center is crucial for enhancing system
designs. Additionally, molecular CO2 reduction catalysts (CO2RCs) must be adapted to operate
under organic conditions, necessitating their compatibility with water-oxidation conditions for
future device design and production (Huang, et al,.2012).

Gold and silver nanoclusters are promising candidates for efficient CO 2 reduction catalysts
(CO2RCs). Their high molecular purity and well-defined atomic structures facilitate a deeper
understanding of the electrocatalytic mechanism involved in CO2 reduction. Moreover, their size
and stable structures contribute to their thermodynamic stability, making them suitable for
practical applications in this field (Ranga, et al,.2019).

An example of successful CO2 reduction catalyst is the Au25(SR)18 nanocluster (where SR =

SCH2CH2Ph). This catalyst has demonstrated under aqueous conditions a remarkable faradaic
efficiency close to 100% for producing CO, with a formation rate 7-700 times higher than
traditional bulk gold-based catalysts (Stoll, et al,.2014).

However, thus far, gold-based clusters have been limited to producing CO. Future research
on Au-based bimetallic clusters is anticipated if researchers intend to generate hydrogenated
products. Additionally, incorporating less expensive metals into gold nanoclusters warrants
further investigation, as this approach shows promise in maximizing metal efficiency while
maintaining catalytic activity (Kitamoto, et al,.2016).

Hybrid catalysts combining methodologies from molecular, material, and biological disciplines
are currently being explored for CO2 reduction catalysis. Enzymes, known for their highly
effective and selective active sites, have demonstrated sustainable energy conversion using
Earth-abundant (Elvington, et al 2016). However, enzymes require a protective protein
environment around their active sites, and replicating this environment poses significant
challenges for researchers aiming to achieve comparable catalytic activity. Despite the challenges
of directly mimicking enzymes, their structures and mechanisms continue to serve as a valuable
blueprint for the design and synthesis of hybrid catalysts (Zigler, et al,.2018).

In hybrid catalysts, elements from biological and material designs, such as high surface
area and porosity, can be integrated into molecular catalysts to optimize active sites, thereby
enhancing rates of CO2 reduction and selectivity ( Huang, et al,.2013). For instance, researchers
have constructed supramolecular cages using tetrapodalporphyrins on copper electrodes,
incorporating amides in porphyrin-copper surface linkers. demonstrated how bioinspired
elements can be integrated into molecular and material designs to enhance selective
CO2 reduction and improve fuel production (Long, et al,.2015). For example, they assembled
supramolecular cages of tetrapodal porphyrins on copper electrodes, utilizing amides
in porphyrin-copper surface linkers to facilitate hydrogen bonding akin to enzymes. Under
optimized conditions, these porphyrin cages exhibited high selectivity, producing 57% ethanol,
24% acetate, and 2% ethylene as high-value C 2 products ( Horton, et al,.2017).This design
exemplifies how bioinspired elements can be integrated into molecular and material designs to
enhance selective CO2 reduction and improve fuel Production (Aro, et al,.2014).
Limitations
Although the concept of mimicking nature to harness solar energy was proposed as early as
1918, significant progress has only been achieved in the last 30 years. Projects funded by the
U.S. Department of Energy have developed highly effective and stable PV-
GDE systems (Demmig, et al,.2012). These systems yield CO with an average energy conversion
efficiency of 18.7% at noon and a maximum efficiency of 19.1%, which is among the highest
reported efficiencies in this field of invention. However, this achievement is fleeting, as the
overall performance still fails to meet the targeted efficiency required for a commercially viable
energy-generating (Barber, et al,.2019). Questions regarding the device's performance under less
sunny conditions and over extended operational periods remain unanswered. Another promising
avenue of research involves a low-cost approach to producing CO using
a photoelectrochemical cell equipped with noble-metal-free catalysts. While this system
achieved a high Faradaic efficiency for the CO 2 reduction module, the overall energy conversion
remains inefficient, indicating the need for further research efforts in this area (Karlsson, et
al,.2012).

Researchers have developed a comprehensive understanding of the water splitting and

water oxidation processes. In contrast, the mechanism for catalyzing CO 2reduction remains
largely unresolved. Despite extensive knowledge and development of water oxidation catalysts,
those that are energetically efficient remain costly and thus require
economic optimisation (Niyogi, et al,.2019).

Future investigations in artificial photosynthesis may focus on several key areas: enhancing
the solar-to-fuel conversion efficiency to improve the yield of existing devices; exploring
alternative methods to produce multielectron-reduced products instead of CO, such as methanol
or methane; and addressing challenges related to sourcing CO 2 and separating CO2-reduced
products in the design of artificial photosynthesis devices. These efforts aim to advance the
efficiency, product range, and practicality of artificial photosynthesis Technologies (Krause, et
al,.2015).

Conclusion
Research into artificial photosynthesis as a renewable energy technology has been ongoing
for decades. Despite the development of numerous techniques, achieving a commercially viable
technology remains elusive. Current technologies encounter bottlenecks such as inadequate
energetic efficiency, limited long-term stability, and high costs. Despite facing significant
challenges, artificial photosynthesis remains a promising technology due to its potential to offer a
compelling solution to the current global energy crisis.

If successfully developed, this technology could significantly reduce humanity's reliance on

fossil fuels and concurrently reduce carbon footprints. Fortunately, researchers have made
substantial progress over the last three decades in understanding the underlying mechanisms of
artificial photosynthesis and in developing various types of catalysts. Researchers have also
made strides in assembling effective and stable models for artificial photosynthesis. The current
challenge lies in bridging knowledge gaps and assembling the missing components necessary for
scalable production. Despite the distance still to cover, recent research advancements provide a
pathway toward envisioning scalable production of this renewable energy technology. It is
hopeful that major installations could become a reality in the upcoming years.