Oxygen evolution

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Oxygenevolution is the process of generating molecular oxygen (O2) by a chemical reaction, usually from water. Oxygen evolution from water is effected by oxygenic photosynthesis, electrolysis of water, and thermal decomposition of various oxides. The biological process supports aerobic life. When relatively pure oxygen is required industrially, it is isolated by distilling liquefied air. [1]

Contents

Oxygen evolution in nature

Photosynthetic oxygen evolution is the fundamental process by which oxygen is generated in the earth's biosphere. The reaction is part of the light-dependent reactions of photosynthesis in cyanobacteria and the chloroplasts of green algae and plants. It utilizes the energy of light to split a water molecule into its protons and electrons for photosynthesis. Free oxygen, generated as a by-product of this reaction, is released into the atmosphere. [2] [3]

Water oxidation is catalyzed by a manganese-containing cofactor contained in photosystem II, known as the oxygen-evolving complex (OEC) or the water-splitting complex. Manganese is an important cofactor, and calcium and chloride are also required for the reaction to occur. [4] The stoichiometry of this reaction is as follows:

2H2O ⟶ 4e− + 4H+ + O2

The protons are released into the thylakoid lumen, thus contributing to the generation of a proton gradient across the thylakoid membrane. This proton gradient is the driving force for adenosine triphosphate (ATP) synthesis via photophosphorylation and the coupling of the absorption of light energy and the oxidation of water for the creation of chemical energy during photosynthesis. [5]

History of discovery

It was not until the end of the 18th century that Joseph Priestley accidentally discovered the ability of plants to "restore" air that had been "injured" by the burning of a candle. He followed up on the experiment by showing that air "restored" by vegetation was "not at all inconvenient to a mouse." He was later awarded a medal for his discoveries that "...no vegetable grows in vain... but cleanses and purifies our atmosphere." Priestley's experiments were further evaluated by Jan Ingenhousz, a Dutch physician, who then showed that the "restoration" of air only worked while in the presence of light and green plant parts. [4]

Water electrolysis

Together with hydrogen (H2), oxygen is evolved by the electrolysis of water. The point of water electrolysis is to store energy in the form of hydrogen gas, a clean-burning fuel. The "oxygen evolution reaction (OER) is the major bottleneck [to water electrolysis] due to the sluggish kinetics of this four-electron transfer reaction." [6] All practical catalysts are heterogeneous.

Diagram showing the overall chemical equation. Electrolysis of Water.png
Diagram showing the overall chemical equation.

Electrons (e−) are transferred from the cathode to protons to form hydrogen gas. The half reaction, balanced with acid, is:

2 H+ + 2e− → H2

At the positively charged anode, an oxidation reaction occurs, generating oxygen gas and releasing electrons to the anode to complete the circuit:

2 H2O → O2 + 4 H+ + 4e−

Combining either half reaction pair yields the same overall decomposition of water into oxygen and hydrogen:

Overall reaction:
2 H2O → 2 H2 + O2

Chemical oxygen generation

Although some metal oxides eventually release O2 when heated, these conversions generally require high temperatures. A few compounds release O2 at mild temperatures. Chemical oxygen generators consist of chemical compounds that release O2 when stimulated, usually by heat. They are used in submarines and commercial aircraft to provide emergency oxygen. Oxygen is generated by the high-temperature decomposition of sodium chlorate: [1]

2 NaClO3 → 2 NaCl + 3 O2

Potassium permanganate also releases oxygen upon heating, but the yield is modest.

2 KMnO4 → MnO2 + K2MnO4 + O2

See also

Related Research Articles

<span class="mw-page-title-main">Hydrogen</span> Chemical element, symbol H and atomic number 1

Hydrogen is the chemical element with the symbol H and atomic number 1. Hydrogen is the lightest element. At standard conditions hydrogen is a gas of diatomic molecules having the formula H2. It is colorless, odorless, tasteless, non-toxic, and highly combustible. Hydrogen is the most abundant chemical substance in the universe, constituting roughly 75% of all normal matter. Stars such as the Sun are mainly composed of hydrogen in the plasma state. Most of the hydrogen on Earth exists in molecular forms such as water and organic compounds. For the most common isotope of hydrogen each atom has one proton, one electron, and no neutrons.

<span class="mw-page-title-main">Photosynthesis</span> Biological process to convert light into chemical energy

Photosynthesis is a biological process used by many cellular organisms to convert light energy into chemical energy, which is stored in organic compounds that can later be metabolized through cellular respiration to fuel the organism's activities. The term usually refers to oxygenic photosynthesis, where oxygen is produced as a byproduct, and some of the chemical energy produced is stored in carbohydrate molecules such as sugars, starch and cellulose, which are synthesized from endergonic reaction of carbon dioxide with water. Most plants, algae and cyanobacteria perform photosynthesis; such organisms are called photoautotrophs. Photosynthesis is largely responsible for producing and maintaining the oxygen content of the Earth's atmosphere, and supplies most of the biological energy necessary for complex life on Earth.

<span class="mw-page-title-main">Electrolysis</span> Technique in chemistry and manufacturing

In chemistry and manufacturing, electrolysis is a technique that uses direct electric current (DC) to drive an otherwise non-spontaneous chemical reaction. Electrolysis is commercially important as a stage in the separation of elements from naturally occurring sources such as ores using an electrolytic cell. The voltage that is needed for electrolysis to occur is called the decomposition potential. The word "lysis" means to separate or break, so in terms, electrolysis would mean "breakdown via electricity".

<span class="mw-page-title-main">Redox</span> Chemical reaction in which oxidation states of atoms are changed

Redox is a type of chemical reaction in which the oxidation states of substrate change. Oxidation is the loss of electrons or an increase in the oxidation state, while reduction is the gain of electrons or a decrease in the oxidation state.

In chemistry, a reducing agent is a chemical species that "donates" an electron to an electron recipient. Examples of substances that are common reducing agents include the alkali metals, formic acid, oxalic acid, and sulfite compounds.

<span class="mw-page-title-main">Thylakoid</span> Membrane enclosed compartments in chloroplasts and cyanobacteria

Thylakoids are membrane-bound compartments inside chloroplasts and cyanobacteria. They are the site of the light-dependent reactions of photosynthesis. Thylakoids consist of a thylakoid membrane surrounding a thylakoid lumen. Chloroplast thylakoids frequently form stacks of disks referred to as grana. Grana are connected by intergranal or stromal thylakoids, which join granum stacks together as a single functional compartment.

A "photoelectrochemical cell" is one of two distinct classes of device. The first produces electrical energy similarly to a dye-sensitized photovoltaic cell, which meets the standard definition of a photovoltaic cell. The second is a photoelectrolytic cell, that is, a device which uses light incident on a photosensitizer, semiconductor, or aqueous metal immersed in an electrolytic solution to directly cause a chemical reaction, for example to produce hydrogen via the electrolysis of water.

<span class="mw-page-title-main">Photosystem</span> Structural units of protein involved in photosynthesis

Photosystems are functional and structural units of protein complexes involved in photosynthesis. Together they carry out the primary photochemistry of photosynthesis: the absorption of light and the transfer of energy and electrons. Photosystems are found in the thylakoid membranes of plants, algae, and cyanobacteria. These membranes are located inside the chloroplasts of plants and algae, and in the cytoplasmic membrane of photosynthetic bacteria. There are two kinds of photosystems: PSI and PSII.

<span class="mw-page-title-main">Photosystem II</span> First protein complex in light-dependent reactions of oxygenic photosynthesis

Photosystem II is the first protein complex in the light-dependent reactions of oxygenic photosynthesis. It is located in the thylakoid membrane of plants, algae, and cyanobacteria. Within the photosystem, enzymes capture photons of light to energize electrons that are then transferred through a variety of coenzymes and cofactors to reduce plastoquinone to plastoquinol. The energized electrons are replaced by oxidizing water to form hydrogen ions and molecular oxygen.

<span class="mw-page-title-main">Photophosphorylation</span> Biochemical process in photosynthesis

In the process of photosynthesis, the phosphorylation of ADP to form ATP using the energy of sunlight is called photophosphorylation. Cyclic photophosphorylation occurs in both aerobic and anaerobic conditions, driven by the main primary source of energy available to living organisms, which is sunlight. All organisms produce a phosphate compound, ATP, which is the universal energy currency of life. In photophosphorylation, light energy is used to pump protons across a biological membrane, mediated by flow of electrons through an electron transport chain. This stores energy in a proton gradient. As the protons flow back through an enzyme called ATP synthase, ATP is generated from ADP and inorganic phosphate. ATP is essential in the Calvin cycle to assist in the synthesis of carbohydrates from carbon dioxide and NADPH.

Artificial photosynthesis is a chemical process that biomimics the natural process of photosynthesis to convert sunlight, water, and carbon dioxide into carbohydrates and oxygen. The term artificial photosynthesis is commonly used to refer to any scheme for capturing and storing the energy from sunlight in the chemical bonds of a fuel. Photocatalytic water splitting converts water into hydrogen and oxygen and is a major research topic of artificial photosynthesis. Light-driven carbon dioxide reduction is another process studied that replicates natural carbon fixation.

<span class="mw-page-title-main">Water splitting</span> Chemical reaction

Water splitting is the chemical reaction in which water is broken down into oxygen and hydrogen:

<span class="mw-page-title-main">Electrolysis of water</span> Electricity-induced chemical reaction

Electrolysis of water is using electricity to split water into oxygen and hydrogen gas by electrolysis. Hydrogen gas released in this way can be used as hydrogen fuel, but must be kept apart from the oxygen as the mixture would be extremely explosive. Separately pressurised into convenient 'tanks' or 'gas bottles', hydrogen can be used for oxyhydrogen welding and other applications, as the hydrogen / oxygen flame can reach circa 2,800°C.

Photodissociation, photolysis, photodecomposition, or photofragmentation is a chemical reaction in which molecules of a chemical compound are broken down by photons. It is defined as the interaction of one or more photons with one target molecule.

<span class="mw-page-title-main">Photosynthetic reaction centre</span> Molecular unit responsible for absorbing light in photosynthesis

A photosynthetic reaction center is a complex of several proteins, pigments and other co-factors that together execute the primary energy conversion reactions of photosynthesis. Molecular excitations, either originating directly from sunlight or transferred as excitation energy via light-harvesting antenna systems, give rise to electron transfer reactions along the path of a series of protein-bound co-factors. These co-factors are light-absorbing molecules (also named chromophores or pigments) such as chlorophyll and pheophytin, as well as quinones. The energy of the photon is used to excite an electron of a pigment. The free energy created is then used, via a chain of nearby electron acceptors, for a transfer of hydrogen atoms (as protons and electrons) from H2O or hydrogen sulfide towards carbon dioxide, eventually producing glucose. These electron transfer steps ultimately result in the conversion of the energy of photons to chemical energy.

<span class="mw-page-title-main">Biohydrogen</span>

Biohydrogen is H2 that is produced biologically. Interest is high in this technology because H2 is a clean fuel and can be readily produced from certain kinds of biomass, including biological waste. Furthermore some photosynthetic microorganisms are capable to produce H2 directly from water splitting using light as energy source.

Dioxygen plays an important role in the energy metabolism of living organisms. Free oxygen is produced in the biosphere through photolysis of water during photosynthesis in cyanobacteria, green algae, and plants. During oxidative phosphorylation in cellular respiration, oxygen is reduced to water, thus closing the biological water-oxygen redox cycle.

<span class="mw-page-title-main">Light-dependent reactions</span> Photosynthetic reactions

Light-dependent reactions is jargon for certain photochemical reactions that are involved in photosynthesis, the main process by which plants acquire energy. There are two light dependent reactions, the first occurs at photosystem II (PSII) and the second occurs at photosystem I (PSI),

Water oxidation is one of the half reactions of water splitting:

<span class="mw-page-title-main">Water oxidation catalysis</span>

Water oxidation catalysis (WOC) is the acceleration (catalysis) of the conversion of water into oxygen and protons:

References

  1. 1 2 Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN   978-0-08-037941-8.
  2. ↑ Yano, Junko; Kern, Jan; Yachandra, Vittal K.; Nilsson, Håkan; Koroidov, Sergey; Messinger, Johannes (2015). "Chapter 2 Light-Dependent Production of Dioxygen in Photosynthesis". In Peter M.H. Kroneck and Martha E. Sosa Torres (ed.). Sustaining Life on Planet Earth: Metalloenzymes Mastering Dioxygen and Other Chewy Gases. Metal Ions in Life Sciences. Vol. 15. Springer. pp. 13–43. doi:10.1007/978-3-319-12415-5_2. PMC   4688042 . PMID   25707465.
  3. ↑ Greife, Paul; Schönborn, Matthias; Capone, Matteo; Assunção, Ricardo; Narzi, Daniele; Guidoni, Leonardo; Dau, Holger (2023). "The electron–proton bottleneck of photosynthetic oxygen evolution". Nature : 1–6. doi: 10.1038/s41586-023-06008-5 .
  4. 1 2 Raven, Peter H.; Ray F. Evert; Susan E. Eichhorn (2005). Biology of Plants, 7th Edition. New York: W.H. Freeman and Company Publishers. pp. 115–127. ISBN   0-7167-1007-2.
  5. ↑ Raval M, Biswal B, Biswal U (2005). "The mystery of oxygen evolution: analysis of structure and function of photosystem II, the water-plastoquinone oxido-reductase". Photosynthesis Research. 85 (3): 267–93. doi:10.1007/s11120-005-8163-4. PMID   16170631. S2CID   12893308.
  6. ↑ Song, Jiajia; Wei, Chao; Huang, Zhen-Feng; Liu, Chuntai; Zeng, Lin; Wang, Xin; Xu, Zhichuan J. (2020). "A Review on Fundamentals for Designing Oxygen Evolution Electrocatalysts". Chemical Society Reviews. 49 (7): 2196–2214. doi:10.1039/C9CS00607A. hdl: 10356/153346 . PMID   32133479. S2CID   212416753.
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