Selective Hydrogenation of Furfural on Ni−P, Ni−B, and Ni−P−B Ultrafine Materials

Abstract

A series of ultafine Ni−P, Ni−B, and Ni−P−B amorphous alloy catalysts with various atomic ratios were prepared by a chemical reduction method. The catalysts were characterized with respect to elemental analysis, nitrogen sorption, XRD, TEM, XPS, and hydrogenation activity. Conventional Raney nickel was included for comparison. The Ni/P/B molar ratio in the starting material significantly affected the concentration of boron and phosphorus bonded to the nickel metal, subsequently affecting the surface area, the amorphous structure, and the hydrogenation activity and selectivity of the catalyst. The different electron transfer between nickel metal and the metalloid elements in Ni−P and Ni−B powders (phosphorus draws electrons and boron donates electrons) results in the extremely different hydrogenation activity of furfural (specific activity per surface area: Ni85.0P15.0 ≫ Ni71.4B28.9). By regulating a suitable P/B ratio, the ultrafine Ni−P−B catalyst dramatically revealed a markedly higher hydrogenation activity of furfural than Ni−P and Ni−B. The specific activities per surface area of the catalyst are in the order Ni74.5P12.1B13.4 > Ni72.5P2.0B25.5 > Ni85.0P15.0 ≫ Ni71.4B28.9 > Raney nickel. The phosphorus is an active component to improve the selectivity of furfuryl alcohol. The hydrogenation of furfural is catalyzed actively by the Ni−P x −B y catalysts, following the first order with respect to the concentration of furfural. The nature of the ultrafine amorphous structure and the P/B ratio are the keys to manipulate the catalytic properties of Ni−P x −B y amorphous alloy catalysts.

Effect of Phosphorus Content on Local Structures of NiP Amorphous Alloys

“…The nano-amorphous Ni-P alloys have gained much attention because of their excellent catalytic activity, better selectivity and strong sulfur resistance for the hydrogen evolution reaction [1][2][3][4][5]. Compared to nano-amorphous Ni-B alloys, Ni-P alloys have higher selectivity and turnover of frequencies (TOF) despite smaller surface area [1,6], showing the potential to represent a new generation of hydrogenation catalysts.…”

“…Compared to nano-amorphous Ni-B alloys, Ni-P alloys have higher selectivity and turnover of frequencies (TOF) despite smaller surface area [1,6], showing the potential to represent a new generation of hydrogenation catalysts. Preparing Ni-P alloys by chemical reduction method has the advantages of low cost and simple technology to be suitably applied in industry.…”

Preparation and catalytic properties of amorphous alloys in hydrogenation of sulfolene

“…Since Smith's first report using amorphous alloy as catalysts in 1980 [1], more and more research work have been done on hydrogenation reactions over amorphous alloys. Up to now, amorphous alloy catalysts have been used in hydrogenation of olefins [2], selective hydrogenation of diene [3][4][5], selective hydrogenation of benzene [6][7][8][9], selective hydrogenation of acetylene in a large excess of ethene [10], hydrogenation of aldehyde and alkones such as furfural [11], glucose [12][13][14] and cinnamaldehyde [15], hydrogenation of nitrobenzene [16,17], selective hydrogenation of nitriles [18][19][20] and hydrogenation of carbon monoxide [21]. In the above reactions, amorphous alloys showed unique catalytic performance, and in many cases they were more active than Raney Ni catalyst.…”

Metal-Free Hydrogenation of Biomass Derived Furfural into Furfuryl Alcohol Over Carbon–MgO Catalysts in Continuous Mode

“…In general, hydrogenation of FU is carried out in either liquid or vapor phase. Various catalytic systems like Ni [2][3][4], Cu [5], CuNi [6] and Co [7] are being used for the selective hydrogenation of FU to FAL in liquid phase. However, hydrogenation of furfural in the vapor phase is preferable to avoid the difficulties in operation and separation.…”