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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 Biomass is plant-based material used as a fuel for heat or electricity production. It can be in the form of wood, wood residues, energy crops, agricultural residues, and waste from industry, farms, and households. Some people use the terms bio ...
. Many challenges characterize this technology, including those intrinsic to H2, such as storage and transportation of a noncondensible gas. Hydrogen producing organisms are poisoned by O2. Yields of H2 are often low.


Biochemical principles

The main reactions involve
fermentation Fermentation is a metabolic process that produces chemical changes in organic substrates through the action of enzymes. In biochemistry, it is narrowly defined as the extraction of energy from carbohydrates in the absence of oxygen. In food p ...
of sugars. Important reactions start with
glucose Glucose is a simple sugar with the molecular formula . Glucose is overall the most abundant monosaccharide, a subcategory of carbohydrates. Glucose is mainly made by plants and most algae during photosynthesis from water and carbon dioxide, u ...
, which is converted to
acetic acid Acetic acid , systematically named ethanoic acid , is an acidic, colourless liquid and organic compound with the chemical formula (also written as , , or ). Vinegar is at least 4% acetic acid by volume, making acetic acid the main componen ...
: :C6H12O6 + 2 H2O -> 2 CH3COOH + 2 CO2 + 4 H2 A related reaction gives
formate Formate (IUPAC name: methanoate) is the conjugate base of formic acid. Formate is an anion () or its derivatives such as ester of formic acid. The salts and esters are generally colorless.Werner Reutemann and Heinz Kieczka "Formic Acid" in ''Ull ...
instead of
carbon dioxide Carbon dioxide ( chemical formula ) is a chemical compound made up of molecules that each have one carbon atom covalently double bonded to two oxygen atoms. It is found in the gas state at room temperature. In the air, carbon dioxide is t ...
: :C6H12O6 + 2 H2O -> 2 CH3COOH + 2 HCOOH + 2 H2 These reactions are exergonic by 216 and 209 kcal/mol, respectively. H2 production is catalyzed by two hydrogenases. One is called eFehydrogenase; the other is called iFehydrogenase. Many organisms express these enzymes. Notable examples are members of the genera
Clostridium ''Clostridium'' is a genus of anaerobic, Gram-positive bacteria. Species of ''Clostridium'' inhabit soils and the intestinal tract of animals, including humans. This genus includes several significant human pathogens, including the causative a ...
,
Desulfovibrio ''Desulfovibrio'' is a genus of Gram-negative sulfate-reducing bacteria. ''Desulfovibrio'' species are commonly found in aquatic environments with high levels of organic material, as well as in water-logged soils, and form major community member ...
,
Ralstonia ''Ralstonia'' is a genus of bacteria, previously included in the genus ''Pseudomonas''. It is named after the American bacteriologist Ericka Ralston. Ericka Ralston was born Ericka Barrett in 1944 in Saratoga, California, and died in 2015 in Seb ...
, and the pathogen ''
Helicobacter ''Helicobacter'' is a genus of Gram-negative bacteria possessing a characteristic helical shape. They were initially considered to be members of the genus ''Campylobacter'', but in 1989, Goodwin ''et al.'' published sufficient reasons to justif ...
''. '' E. coli'' is the workhorse for genetic engineering of hydrogenases. It has been estimated that 99% of all organisms utilize
dihydrogen 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 . It is colorless, odorless, tasteless, non-toxic, ...
(H2). Most of these species are microbes and their ability to use H2 as a metabolite arises from the expression of H2 metalloenzymes known as hydrogenases. Hydrogenases are sub-classified into three different types based on the active site metal content: iron-iron hydrogenase, nickel-iron hydrogenase, and iron hydrogenase.


Production by algae

The biological hydrogen production with
algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular micr ...
is a method of photobiological
water splitting Water splitting is the chemical reaction in which water is broken down into oxygen and hydrogen: :2 H2O → 2 H2 + O2 Efficient and economical water splitting would be a technological breakthrough that could underpin a hydrogen economy, base ...
which is done in a
closed Closed may refer to: Mathematics * Closure (mathematics), a set, along with operations, for which applying those operations on members always results in a member of the set * Closed set, a set which contains all its limit points * Closed interval, ...
photobioreactor Moss photobioreactor to cultivate Physcomitrella_patens.html"_;"title="mosses_like_''Physcomitrella_patens">mosses_like_''Physcomitrella_patens''_at_the_laboratory_scale A_photobioreactor_(PBR)_refers_to_any_cultivation_system_designed_for_growin ...
based on the
production of hydrogen Hydrogen production is the family of industrial methods for generating hydrogen gas. As of 2020, the majority of hydrogen (∼95%) is produced from fossil fuels by steam reforming of natural gas and other light hydrocarbons, partial oxidation o ...
as a
solar fuel A solar fuel is a synthetic chemical fuel produced from solar energy. Solar fuels can be produced through photochemical (i.e. activation of certain chemical reactions by Photon, photons), photobiological (i.e., artificial photosynthesis), thermoch ...
by
algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular micr ...
.
Algae Algae (; singular alga ) is an informal term for a large and diverse group of photosynthetic eukaryotic organisms. It is a polyphyletic grouping that includes species from multiple distinct clades. Included organisms range from unicellular micr ...
produce hydrogen under certain conditions. In 2000 it was discovered that if '' C. reinhardtii'' algae are deprived of
sulfur Sulfur (or sulphur in British English) is a chemical element with the symbol S and atomic number 16. It is abundant, multivalent and nonmetallic. Under normal conditions, sulfur atoms form cyclic octatomic molecules with a chemical formul ...
they will switch from the production of
oxygen Oxygen is the chemical element with the symbol O and atomic number 8. It is a member of the chalcogen group in the periodic table, a highly reactive nonmetal, and an oxidizing agent that readily forms oxides with most elements ...
, as in normal
photosynthesis Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored in ...
, to the production of hydrogen.


Photosynthesis

Photosynthesis Photosynthesis is a process used by plants and other organisms to convert light energy into chemical energy that, through cellular respiration, can later be released to fuel the organism's activities. Some of this chemical energy is stored in ...
in
cyanobacteria Cyanobacteria (), also known as Cyanophyta, are a phylum of gram-negative bacteria that obtain energy via photosynthesis. The name ''cyanobacteria'' refers to their color (), which similarly forms the basis of cyanobacteria's common name, bl ...
and
green algae The green algae (singular: green alga) are a group consisting of the Prasinodermophyta and its unnamed sister which contains the Chlorophyta and Charophyta/ Streptophyta. The land plants (Embryophytes) have emerged deep in the Charophyte alga ...
splits water into hydrogen ions and electrons. The electrons are transported over
ferredoxin Ferredoxins (from Latin ''ferrum'': iron + redox, often abbreviated "fd") are iron–sulfur proteins that mediate electron transfer in a range of metabolic reactions. The term "ferredoxin" was coined by D.C. Wharton of the DuPont Co. and applied t ...
s. Fe-Fe-hydrogenases (enzymes) combine them into hydrogen gas. In ''Chlamydomonas reinhardtii''
Photosystem II Photosystem II (or water-plastoquinone oxidoreductase) 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 photosyst ...
produces in direct conversion of sunlight 80% of the electrons that end up in the hydrogen gas. Light-harvesting complex
photosystem II light-harvesting protein 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 ...
LHCBM9 promotes efficient light energy dissipation. The Fe-Fe-hydrogenases need an
anaerobic Anaerobic means "living, active, occurring, or existing in the absence of free oxygen", as opposed to aerobic which means "living, active, or occurring only in the presence of oxygen." Anaerobic may also refer to: * Anaerobic adhesive, a bonding a ...
environment as they are inactivated by oxygen.
Fourier transform infrared spectroscopy Fourier-transform infrared spectroscopy (FTIR) is a technique used to obtain an infrared spectrum of absorption or emission of a solid, liquid, or gas. An FTIR spectrometer simultaneously collects high-resolution spectral data over a wide spectra ...
is used to examine metabolic pathways. In 2020 scientists reported the development of algal-cell based micro-droplets for multicellular
spheroid A spheroid, also known as an ellipsoid of revolution or rotational ellipsoid, is a quadric surface obtained by rotating an ellipse about one of its principal axes; in other words, an ellipsoid with two equal semi-diameters. A spheroid has ...
microbial reactors capable of producing
hydrogen 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 . It is colorless, odorless, tasteless, non-to ...
alongside either oxygen or CO2 via photosynthesis in daylight under air. Enclosing the microreactors with synergistic bacteria was shown to increase levels of hydrogen production. Available unde
CC BY 4.0


Specialized chlorophyll

The
chlorophyll Chlorophyll (also chlorophyl) is any of several related green pigments found in cyanobacteria and in the chloroplasts of algae and plants. Its name is derived from the Greek words , ("pale green") and , ("leaf"). Chlorophyll allow plants to ...
(Chl) antenna size in green algae is minimized, or truncated, to maximize photobiological solar conversion efficiency and H2 production. The truncated Chl antenna size minimizes absorption and wasteful dissipation of sunlight by individual cells, resulting in better light utilization efficiency and greater photosynthetic productivity by the green alga mass culture.


Economics

It would take about 25,000 square kilometre algal farming to produce biohydrogen equivalent to the energy provided by gasoline in the US alone. This area represents approximately 10% of the area devoted to growing soya in the US.


Bioreactor design issues

* Restriction of photosynthetic hydrogen production by accumulation of a
proton gradient An electrochemical gradient is a gradient of electrochemical potential, usually for an ion that can move across a membrane. The gradient consists of two parts, the chemical gradient, or difference in solute concentration across a membrane, and ...
. * Competitive inhibition of photosynthetic hydrogen production by carbon dioxide. * Requirement for bicarbonate binding at
photosystem II Photosystem II (or water-plastoquinone oxidoreductase) 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 photosyst ...
(PSII) for efficient photosynthetic activity. * Competitive drainage of electrons by oxygen in algal hydrogen production. * Economics must reach competitive price to other sources of energy and the economics are dependent on several parameters. * A major technical obstacle is the efficiency in converting solar energy into chemical energy stored in molecular hydrogen. Attempts are in progress to solve these problems via
bioengineering Biological engineering or bioengineering is the application of principles of biology and the tools of engineering to create usable, tangible, economically-viable products. Biological engineering employs knowledge and expertise from a number o ...
.


History

In 1933,
Marjory Stephenson Marjory Stephenson (24 January 1885 – 12 December 1948) was a British biochemist. In 1945, she was one of the first two women elected a Fellow of the Royal Society, the other being Kathleen Lonsdale. She wrote ''Bacterial Metabolism'' (193 ...
and her student Stickland reported that cell suspensions catalysed the reduction of
methylene blue Methylthioninium chloride, commonly called methylene blue, is a salt used as a dye and as a medication. Methylene blue is a thiazine dye. As a medication, it is mainly used to treat methemoglobinemia by converting the ferric iron in hemoglobin ...
with H2. Six years later,
Hans Gaffron Dr. Hans Gaffron was born in Lima, Peru, on May 17, 1902, and was a son of the German physician Eduard Gaffron and his wife Hedwig von Gevekot. He was one of the earlier researchers trying to elucidate the mechanistic and biochemical details of ...
observed that the green photosynthetic alga ''
Chlamydomonas reinhardtii ''Chlamydomonas reinhardtii'' is a single-cell green alga about 10 micrometres in diameter that swims with two flagella. It has a cell wall made of hydroxyproline-rich glycoproteins, a large cup-shaped chloroplast, a large pyrenoid, and an eye ...
'', would sometimes produce hydrogen. In the late 1990s Anastasios Melis discovered that deprivation of sulfur induces the alga to switch from the production of oxygen (normal photosynthesis) to the production of hydrogen. He found that the
enzyme Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
responsible for this reaction is hydrogenase, but that the hydrogenase lost this function in the presence of oxygen. Melis also discovered that depleting the amount of sulfur available to the algae interrupted their internal oxygen flow, allowing the hydrogenase an environment in which it can react, causing the algae to produce hydrogen. ''Chlamydomonas moewusii'' is also a promising strain for the production of hydrogen.


Industrial hydrogen

Competing for biohydrogen, at least for commercial applications, are many mature industrial processes.
Steam reforming Steam reforming or steam methane reforming (SMR) is a method for producing syngas (hydrogen and carbon monoxide) by reaction of hydrocarbons with water. Commonly natural gas is the feedstock. The main purpose of this technology is hydrogen product ...
of
natural gas Natural gas (also called fossil gas or simply gas) is a naturally occurring mixture of gaseous hydrocarbons consisting primarily of methane in addition to various smaller amounts of other higher alkanes. Low levels of trace gases like carbon d ...
- sometimes referred to as steam methane reforming (SMR) - is the most common method of producing bulk hydrogen at about 95% of the world production. :CH4 + H2O <-> CO + 3 H2


See also

*
Algaculture Algaculture is a form of aquaculture involving the farming of species of algae. The majority of algae that are intentionally cultivated fall into the category of microalgae (also referred to as phytoplankton, microphytes, or planktonic algae). Mac ...
*
Hydrogen production Hydrogen production is the family of industrial methods for generating hydrogen gas. As of 2020, the majority of hydrogen (∼95%) is produced from fossil fuels by steam reforming of natural gas and other light hydrocarbons, partial oxidation of ...
* Hydrogenase * Photohydrogen * Timeline of hydrogen technologies


References


External links


DOE - A Prospectus for Biological Production of HydrogenMaximizing Light Utilization Efficiency and Hydrogen Production in Microalgal CulturesDIY Algae/Hydrogen Bioreactor 2004EERE-CYCLIC PHOTOBIOLOGICAL ALGAL H2-PRODUCTION
{{Environmental technology Anaerobic digestion Biodegradable waste management Biodegradation Biofuels Biotechnology products Fuel gas Fuels Hydrogen Hydrogen biology Hydrogen economy Hydrogen production Waste management