Electro and photoreduction of CO 2 driven by manganese-carbonyl molecular catalysts

Photo‐Assisted Electrocatalytic Reduction of CO2: A New Strategy for Reducing Catalytic Overpotentials

“…To our knowledge, this is a unique, yet unexplored way to address the sometimes rather negative reduction potentials along the reduction path of these complexes needed to generate the electrocatalyst, which we have termed as photo-assisted electrochemical reduction. In recent years, catalysts based on the unsustainable Earth-rare metals (Re, Ru, Rh, Ir) [2] have been relegated to benchmark status, as the community refocuses efforts on the Earth-abundant metals such as Mn, [10][11][12][13][14][15] Fe [16][17][18] and more recently the Group-6 triad (Cr, Mo, W). [19][20][21][22][23][24][25][26] For this reason, two viable catalyst precursors, fac-[Mn(CO) 3 (bipy)Br] (1) and [Mo(CO) 4 (6,6'-dmbipy)] (6,6'-dmbipy = 6,6'-dimethyl-2,2'-bipyridine) (2) have been selected for this investigation.…”

Local ionic liquid environment at a modified iron porphyrin catalyst enhances the electrocatalytic performance of CO2 to CO reduction in water

“…[1][2][3][4][5][6] Molecular chemistry offers many handles to implement several tactics for the development and optimization of catalysts. [7][8][9][10][11][12][13][14][15][16] Iron porphyrin derivatives have been shown to be highly performing catalysts for the reduction of CO 2 to CO. 17,18 Hinging on this finding, development of more sophisticated porphyrin macrocycles holding functional groups such as proton donors or cationic units in the second coordination sphere has contributed to lowering the overpotential of this energetically demanding reaction and also to enhancing the catalytic turnover numbers and frequencies. [19][20][21] However, a recent finding that zinc porphyrins can also manage the reduction of CO 2 to CO has brought new perspectives in considering the redox participation of the porphyrin macrocycle in the observed catalytic reactivity.…”

Solar-driven CO2 to CO reduction utilizing H2O as an electron donor by earth-abundant Mn–bipyridine complex and Ni-modified Fe-oxyhydroxide catalysts activated in a single-compartment reactor

“…Many Mn-complexes have been reported for electrochemical or photocatalytic CO 2 reduction. [9][10][11][12] We have reported that a Mn-complex polymer (hereinafter referred to as [Mn-MeCN]) on multi-walled carbon nanotubes (MWCNTs) facilitated electrocatalytic CO 2 reduction in a mixed aqueous solution of potassium borate and sulfate (hereinafter referred to as KBB) with near neutral pH, while the bare Mn-complex did not function as a catalyst in the same solution. 11 The overpotential of electrocatalytic CO 2 reduction over [Mn-MeCN] was significantly reduced to 100 mV by the synergetic effect of the MWCNT support and K + cations.…”