A radiolytic electrochemical system comprising: (a) a cathode; (b) an anode that comprises: (i) a semiconductor component having a nanoscale morphology that comprises nanopores having an average diameter in a range from 10 nm to 500 nm, wherein the nanopores are spaced a distance apart that is in a range from 10 nm to 500 μm; (ii) a conduction component comprising an ohmic metal in contact with the semiconductor component thereby forming a non-rectifying metal-semiconductor junction; the ohmic metal being selected from the group consisting of Al, Ag, Ti, Ni, Au, Fe, Cr, Pt, Pb, Mo, and Cu, alloys thereof, and combinations of the foregoing metallic elements and/or alloys; and (iii) a Schottky component having a thickness in a range from 1 nm to 100 nm, said Schottky component comprising a Schottky component metal in contact with the semiconductor component, thereby forming a rectifying metal-semiconductor junction; wherein the Schottky component has a nanoscale morphology comprising nanopores of an average diameter in a range from 10 nm to 500 nm; (c) an aqueous electrolyte solution in contact with the cathode and the anode, but not the conduction component of the anode; and (d) a ionizing radiation source that is a beta particle emitting radioisotope selected from the group consisting of 63 Ni, 90 Sr, 35 S, 204 Tl, and 3 H, 148 Gd, and 137 Cs or an alpha particle emitting radioisotope selected from the group consisting of 210 Po, 244 Cm, 238 Pu, and 241 Am. (a) a cathode; (b) an anode that comprises: (i) a semiconductor component having a nanoscale morphology that comprises nanopores having an average diameter in a range from 10 nm to 500 nm, wherein the nanopores are spaced a distance apart that is in a range from 10 nm to 500 μm; (ii) a conduction component comprising an ohmic metal in contact with the semiconductor component thereby forming a non-rectifying metal-semiconductor junction; the ohmic metal being selected from the group consisting of Al, Ag, Ti, Ni, Au, Fe, Cr, Pt, Pb, Mo, and Cu, alloys thereof, and combinations of the foregoing metallic elements and/or alloys; and (iii) a Schottky component having a thickness in a range from 1 nm to 100 nm, said Schottky component comprising a Schottky component metal in contact with the semiconductor component, thereby forming a rectifying metal-semiconductor junction; wherein the Schottky component has a nanoscale morphology comprising nanopores of an average diameter in a range from 10 nm to 500 nm; (i) a semiconductor component having a nanoscale morphology that comprises nanopores having an average diameter in a range from 10 nm to 500 nm, wherein the nanopores are spaced a distance apart that is in a range from 10 nm to 500 μm; (ii) a conduction component comprising an ohmic metal in contact with the semiconductor component thereby forming a non-rectifying metal-semiconductor junction; the ohmic metal being selected from the group consisting of Al, Ag, Ti, Ni, Au, Fe, Cr, Pt, Pb, Mo, and Cu, alloys thereof, and combinations of the foregoing metallic elements and/or alloys; and (iii) a Schottky component having a thickness in a range from 1 nm to 100 nm, said Schottky component comprising a Schottky component metal in contact with the semiconductor component, thereby forming a rectifying metal-semiconductor junction; wherein the Schottky component has a nanoscale morphology comprising nanopores of an average diameter in a range from 10 nm to 500 nm; (c) an aqueous electrolyte solution in contact with the cathode and the anode, but not the conduction component of the anode; and (d) a ionizing radiation source that is a beta particle emitting radioisotope selected from the group consisting of 63 Ni, 90 Sr, 35 S, 204 Tl, and 3 H, 148 Gd, and 137 Cs or an alpha particle emitting radioisotope selected from the group consisting of 210 Po, 244 Cm, 238 Pu, and 241 Am.