《厦门大学学报（自然科学版）》

甲酸(FA)分解制氢是解决能源问题的有效途径,而开发一类高效、稳定、廉价的催化剂是FA分解制氢在未来得到广泛应用的关键.联合使用一水合次亚磷酸钠(NaH2PO2·H2O)和二甲胺硼烷(DMAB)作为还原剂,成功制备了一类B、P共掺杂的Pd基催化剂,其对FA分解制氢具有较高的活性和选择性.在303 K、反应混合液为1 mol/L FA和3 mol/L甲酸钠(SF)的条件下,前1 h反应的平均转化频率(TOF)达到798 h-1,通过气相色谱检测发现分解后的气体产物中CO的体积分数小于0.01%,保证了分解得到氢气的清洁.

Dehydrogenation via formic acid decomposition is an effective way to solve energy problem,and the development of a class of highly efficient,stable and cheap catalyst is the key to extensive applications of formic acid dehydrogenation in the future.In this paper,a new kind of double doped Pd-based catalyst(Pd-B-P/C)were successfully prepared by using hydrated sodium hypophosphite and dimethylamine borane(DMAB)as reducing agent,which displayed high activity and selectivity for decomposition of formic acid.Under optional reaction conditions:303 K,1 mol/L formic acid and 3 mol/L sodium formate,the turn-over frequency(TOF)of formic acid decomposition over the Pd-B-P/C catalyst reached 798 h-1 in the first 1 hour.The gas products from decomposition of the formic acid were measured by gas chromatography and found that the fractional volume of CO was less than 0.01%,which ensured the decomposed hydrogen clean and pure.

引言
1 实验部分
2 结果与讨论
3 结论

图1 不同催化剂催化FA分解的催化活性<br/>Fig.1 Activities of different catalysts for FA decomposition

图1 不同催化剂催化FA分解的催化活性
Fig.1 Activities of different catalysts for FA decomposition

图2 不同催化剂的XRD谱图<br/>Fig.2 XRD patterns of different catalysts

图2 不同催化剂的XRD谱图
Fig.2 XRD patterns of different catalysts

图3 Pd/C和Pd-P/C(a)以及Pd-B/C和Pd-B-P/C(b)催化剂的Pd-3d的XPS谱图<br/>Fig.3 XPS spectra of Pd-3d of the catalysts Pd/C and Pd-P/C(a),Pd-B/C and Pd-B-P/C(b)

图3 Pd/C和Pd-P/C(a)以及Pd-B/C和Pd-B-P/C(b)催化剂的Pd-3d的XPS谱图
Fig.3 XPS spectra of Pd-3d of the catalysts Pd/C and Pd-P/C(a),Pd-B/C and Pd-B-P/C(b)

图4 不同FA和SF总浓度条件下催化分解的活性(a)和不同FA和SF浓度比下反应的TOF(b)<br/>Fig.4 Catalytic activities under different concentrations of FA-SF solutions(a); and plot of TOF versus concentration ratio of FA and SF(b)

图4 不同FA和SF总浓度条件下催化分解的活性(a)和不同FA和SF浓度比下反应的TOF(b)
Fig.4 Catalytic activities under different concentrations of FA-SF solutions(a); and plot of TOF versus concentration ratio of FA and SF(b)

图5 Pd/C(a)、Pd-P/C(b)、Pd-B/C(c)和Pd-B-P/C(d)催化下ln TOF对T-1曲线<br/>Fig.5 Arrhrnius plot(ln TOF vs T-1)catalyzed by Pd/C(a),Pd-P/C(b),Pd-B/C(c)and Pd-B-P/C(d)

图5 Pd/C(a)、Pd-P/C(b)、Pd-B/C(c)和Pd-B-P/C(d)催化下ln TOF对T-1曲线
Fig.5 Arrhrnius plot(ln TOF vs T-1)catalyzed by Pd/C(a),Pd-P/C(b),Pd-B/C(c)and Pd-B-P/C(d)

表1 不同催化体系下FA分解反应的TOF和活化能<br/>Tab.1 TOF and Ea values for decomposition of FA catalyzed by various catalyst systems

表1 不同催化体系下FA分解反应的TOF和活化能
Tab.1 TOF and Ea values for decomposition of FA catalyzed by various catalyst systems

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备注

引言

1 实验部分

2 结果与讨论

3 结论

学报简介

备注

引言

1 实验部分

2 结果与讨论

3 结 论

学报简介

3 结论