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Reverse electrodialysis allows for the capture of energy from salinity gradients between salt and fresh waters, but potential applications are currently limited to coastal areas and the need for a large number of membrane pairs. Using salt solutions that could be continuously regenerated with waste heat (≥40°C) and conventional technologies would allow much wider applications of salinity-gradient power production. We used reverse electrodialysis ion-exchange membrane stacks in microbial reverse-electrodialysis cells to efficiently capture salinity-gradient energy from ammonium bicarbonate salt solutions. The maximum power density using acetate reached 5.6 watts per square meter of cathode surface area, which was five times that produced without the dialysis stack, and 3.0 ± 0.05 watts per square meter with domestic wastewater. Maximum energy recovery with acetate reached 30 ± 0.5%.

There is a proactive interest in recovering water, nutrients and energy from waste streams with the increase in municipal wastewater volumes and innovations in resource recovery. Based on the synthesis of wastewater data, this study provides insights into the global and regional “potential” of wastewater as water, nutrient and energy sources while acknowledging the limitations of current resource recovery opportunities and promoting efforts to fast‐track high‐efficiency returns. The study estimates suggest that, currently, 380 billion m3 (m3 = 1,000 L) of wastewater are produced annually across the world which is a volume five‐fold the volume of water passing through Niagara Falls annually. Wastewater production globally is expected to increase by 24% by 2030 and 51% by 2050 over the current level. Among major nutrients, 16.6 Tg (Tg = million metric ton) of nitrogen are embedded in wastewater produced worldwide annually; phosphorus stands at 3.0 Tg and potassium at 6.3 Tg. The full nutrient recovery from wastewater would offset 13.4% of the global demand for these nutrients in agriculture. Beyond nutrient recovery and economic gains, there are critical environmental benefits, such as minimizing eutrophication. At the energy front, the energy embedded in wastewater would be enough to provide electricity to 158 million households. These estimates and projections are based on the maximum theoretical amounts of water, nutrients and energy that exist in the reported municipal wastewater produced worldwide annually. Supporting resource recovery from wastewater will need a step‐wise approach to address a range of constraints to deliver a high rate of return in direct support of Sustainable Development Goals (SDG) 6, 7 and 12, but also other Goals, including adaptation to climate change and efforts in advancing “net‐zero” energy processes towards a green economy.

There is a tremendous source of entropic energy available from the salinity difference between river water and seawater, but this energy has yet to be efficiently captured and stored. Here we demonstrate that H 2 can be produced in a single process by capturing the salinity driven energy along with organic matter degradation using exoelectrogenic bacteria. Only five pairs of seawater and river water cells were sandwiched between an anode, containing exoelectrogenic bacteria, and a cathode, forming a microbial reverse-electrodialysis electrolysis cell. Exoelectrogens added an electrical potential from acetate oxidation and reduced the anode overpotential, while the reverse electrodialysis stack contributed 0.5-0.6 V at a salinity ratio (seawater:river water) of 50. The H 2 production rate increased from 0.8 to 1.6 m 3 -H 2 ∕m 3 -anolyte/day for seawater and river water flow rates ranging from 0.1 to 0.8 mL∕ min. H 2 recovery, the ratio of electrons used for H 2 evolution to electrons released by substrate oxidation, ranged from 72% to 86%. Energy efficiencies, calculated from changes in salinities and the loss of organic matter, were 58% to 64%. By using a relatively small reverse electrodialysis stack (11 membranes), only ∼1% of the produced energy was needed for pumping water. Although Pt was used on the cathode in these tests, additional tests with a nonprecious metal catalyst (MoS 2 ) demonstrated H 2 production at a rate of 0.8 m 3 ∕m 3 ∕d and an energy efficiency of 51%. These results show that pure H 2 gas can efficiently be produced from virtually limitless supplies of seawater and river water, and biodegradable organic matter.electrohydrogenesis | microbial electrolysis cell | microbial fuel cell | renewable energy | sustainable energy E xoelectrogenic bacteria oxidize organic matter and can transfer electrons to electrically conductive materials such as graphite or metal, making it possible to convert waste organic matter into useful energy. In microbial fuel cells (MFCs), exoelectrogens on the anode, coupled with oxygen reduction at the cathode, can generate a potential as large as ∼0.8 V (open circuit; pH 7; 0.2 atm O 2 ), although less voltage (∼0.23 to 0.5 V) is generated in practice (1). Exoelectrogens can also be used to drive electrochemical H 2 production in a microbial electrolysis cell (MEC) (2, 3). However, the potential generated by substrate oxidation (−0.30 V vs. Standard Hydrogen Electrode; 1 g∕L acetate; pH 7) is not sufficient to drive H 2 evolution (−0.41 V vs. Standard Hydrogen Electrode at pH 7) (1). Thus, additional energy (∼0.11 V in theory) is needed to overcome this thermodynamic threshold, and an external voltage of >0.4 V is typically applied to MECs (4). This additional energy could be provided by a renewable source of energy, such as solar (5), wind, or waste organic matter (6). However, no method has yet been developed to directly achieve H 2 production in one process without an external voltage supply.Reverse electrodialysis (RED) holds great promise as a method for generat...

A new type of bioelectrochemical system for producing electrical power, called a microbial reverse-electrodialysis cell (MRC), was developed to increase voltages and power densities compared to those generated individually by microbial fuel cells (MFCs) or reverse electrodialysis (RED) systems. In RED systems, electrode overpotentials create significant energy losses due to thermodynamically unfavorable electrode reactions, and therefore a large number of stacked cells must be used to have significant energy recovery. This results in high capital costs for the large number of membranes, and increases energy losses from pumping water through a large number of cells. In an MRC, high overpotentials are avoided through oxidation of organic matter by exoelectrogenic bacteria on the anode and oxygen reduction on the cathode. An MRC containing only five pairs of RED cells, fed solutions typical of seawater (600 mM NaCl) and river water (12 mM NaCl) at 0.85 mL/min, produced up to 3.6 W/m(2) (cathode surface area) and 1.2-1.3 V with acetate as a substrate. Pumping accounted for <2% of the produced power. A higher flow rate (1.55 mL/min) increased power densities up to 4.3 W/m(2). COD removal was 98% with a Coulombic efficiency of 64%. Power production by the individual components was substantially lower with 0.7 W/m(2) without salinity driven energy, and <0.015 W/m(2) with reduced exoelectrogenic activity due to substrate depletion. These results show that the combination of an MFC and a RED stack synergistically increases performance relative to the individual systems, producing a new type of system that can be used to more efficiently capture salinity driven energy from seawater and river water.

A microbial desalination cell (MDC) is a new approach for desalinating water based on using the electrical current generated by exoelectrogenic bacteria. Previously developed MDCs have used only one or two desalination chambers with substantial internal resistance, and used low salinity catholytes containing a buffered or acid solution. Here we show that substantially improved MDC performance can be obtained even with a nonbuffered, saline catholyte, by using an electrodialysis stack consisting of 5 pairs of desalting and concentrating cells. When 4 stacked MDCs were used in series (20 total pairs of desalination chambers), the salinity of 0.06 L of synthetic seawater (35 g/L NaCl) was reduced by 44% using 0.12 L of anode solution (2:1). The resistive loss in the electrodialysis stack was negligible due to minimization of the intermembrane distances, and therefore the power densities produced by the MDC were similar to those produced by single chamber microbial fuel cells (MFCs) lacking desalination chambers. The observed current efficiency was 86%, indicating separation of 4.3 pairs of sodium and chloride ions for every electron transferred through the circuit. With two additional stages (total of 3.8 L of anolyte), desalination was increased to 98% salt removal, producing 0.3 L of fresh water (12.6:1). These results demonstrate that stacked MDCs can be used for efficient desalination of seawater while at the same time achieving power densities comparable to those obtained in MFCs.

Voltages produced by microbial fuel cells (MFCs) cannot be sustainably increased by linking them in series due to voltage reversal, which substantially reduces stack voltages. It was shown here that MFC voltages can be increased with continuous power production using an electronic circuit containing two sets of multiple capacitors that were alternately charged and discharged (every one second). Capacitors were charged in parallel by the MFCs, but linked in series while discharging to the circuit load (resistor). The parallel charging of the capacitors avoided voltage reversal, while discharging the capacitors in series produced up to 2.5 V with four capacitors. There were negligible energy losses in the circuit compared to 20-40% losses typically obtained with MFCs using DC-DC converters to increase voltage. Coulombic efficiencies were 67% when power was generated via four capacitors, compared to only 38% when individual MFCs were operated with a fixed resistance of 250 U. The maximum power produced using the capacitors was not adversely affected by variable performance of the MFCs, showing that power generation can be maintained even if individual MFCs perform differently. Longer capacitor charging and discharging cycles of up to 4 min maintained the average power but increased peak power by up to 2.6 times. These results show that capacitors can be used to easily obtain higher voltages from MFCs, allowing for more useful capture of energy from arrays of MFCs.

Hydrogen gas can be electrochemically produced in microbial reverse-electrodialysis electrolysis cells (MRECs) using current derived from organic matter and salinity-gradient energy such as river water and seawater solutions. Here, it is shown that ammonium bicarbonate salts, which can be regenerated using low-temperature waste heat, can also produce sufficient voltage for hydrogen gas generation in an MREC. The maximum hydrogen production rate was 1.6 m 3 H 2 /m 3 ·d, with a hydrogen yield of 3.4 mol H 2 / mol acetate at a salinity ratio of infinite. Energy recovery was 10% based on total energy applied with an energy efficiency of 22% based on the consumed energy in the reactor. The cathode overpotential was dependent on the catholyte (sodium bicarbonate) concentration, but not the salinity ratio, indicating high catholyte conductivity was essential for maximizing hydrogen production rates. The direction of the HC and LC flows (co-or countercurrent) did not affect performance in terms of hydrogen gas volume, production rates, or stack voltages. These results show that the MREC can be successfully operated using ammonium bicarbonate salts that can be regenerated using conventional distillation technologies and waste heat making the MREC a useful method for hydrogen gas production from wastes. ■ INTRODUCTIONHydrogen gas can be electrochemically produced at the cathode in a microbial electrolysis cell (MEC) from current generated using microorganisms at the anode by adding a voltage (>0.11 V using acetate) that is theoretically much less than that needed to split water (>1.2 V).1 In practice, the applied voltages are much higher and typically 0.4 to 1 V, substantially lowering the possible overall energy recovery.2 A renewable source of the electrical power is needed for applying this added voltage to make the MEC a green and sustainable method of hydrogen production.It was recently shown that salinity-gradient energy could be harnessed as the source of voltage needed to enable hydrogen gas production.3 Reverse electodialysis (RED) is a method for converting salinity differences between seawater and river water into electrical power. The RED stack consists of a series of alternating anion exchange membranes (AEMs) and cation exchange membranes (CEMs) that dictate the direction of the flow of positive or negative ions from the high salinity solution creating a method to convert an electrochemical potential into electrical current. In a RED system, seawater and river water are pumped between the membranes in a stack that can contain ∼20 or more membrane pairs (∼0.1 to 0.2 V per membrane pair) to generate sufficient potential to split water. 4,5 However, by incorporating a RED stack of only ∼5 membrane pairs between the electrodes in an MEC, it is possible to both avoid the need to split water and also to eliminate the need for an external power source for hydrogen gas production. This combined MEC and RED process, called a microbial reverseelectrodialysis electrolysis cell (MREC), was recently shown to pr...